CN1138326A - N-substituted aryl trifluoromethyl imidazoles - Google Patents

N-substituted aryl trifluoromethyl imidazoles Download PDF

Info

Publication number
CN1138326A
CN1138326A CN94194606A CN94194606A CN1138326A CN 1138326 A CN1138326 A CN 1138326A CN 94194606 A CN94194606 A CN 94194606A CN 94194606 A CN94194606 A CN 94194606A CN 1138326 A CN1138326 A CN 1138326A
Authority
CN
China
Prior art keywords
formula
phenyl
alkyl
definition
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN94194606A
Other languages
Chinese (zh)
Inventor
M·海尔
N·雷
A·马霍尔德
C·艾德伦
U·瓦兴多夫-努曼
A·图尔堡
N·曼克
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of CN1138326A publication Critical patent/CN1138326A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/68—Halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/91—Nitro radicals
    • C07D233/92—Nitro radicals attached in position 4 or 5

Landscapes

  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Agronomy & Crop Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oncology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Communicable Diseases (AREA)
  • Medicinal Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention relates to novel N-substituted aryl trifluoromethyl imidazoles of the formula (I) in which Ar is possibly substituted aryl, W is halogen alkyl, R is possibly substituted aryl or one of the radicals -OR<1>, -SR<1>, -N(R<2>)CO2R<3>, and Y is halogen, trifluoromethyl, cyano, nitro, one of the radicals -CONR<4>R<5> or -S(O)nR<6> or possibly substituted aryl, while R<1> to R<6> have the meaning given in the description, a process for producing them, their use as pest-control agents and intermediate products.

Description

Aryl-trifluoromethyl imidazoles that N-replaces
The present invention relates to new N-substituted aryl-trifluoromethyl imidazoles, their preparation method and intermediate, and they are as the application of agricultural chemicals.
Disclose some halo imidazoles in the prior art and had insecticidal property (referring to JP 6,293 279).Yet the activity of these known compounds can not make us satisfied fully in some cases, and is particularly all the more so when using with lower concentration active compound and low amount of application.
Have now found that new formula (I) N-substituted aryl-trifluoromethyl imidazoles:
Figure A9419460600181
Wherein Ar represents the aryl that replaces arbitrarily, and W represents haloalkyl, one of the aryl of any replacement of R representative or following radicals :-OR 1,-SR 1Or
-N (R 2) COR 3And Y represents halogen, trifluoromethyl, nitro ,-S (O) nR 6Or the aryl that replaces arbitrarily,
In addition, when Y is positioned on the C-2 position of imidazole ring, also represent CN or-CONR 4R 5, R wherein 1The following radicals of representing hydrogen or representative to replace arbitrarily: alkyl, cycloalkyl, alkenyl, chain
Alkynyl, aryl or aralkyl, R 2The aryl of representing hydrogen, alkyl, haloalkyl, cycloalkyl or replacing arbitrarily, R 3Representative (X) mR 7, X represent O, S or-NR 8, m represents 0 or 1, R 4, R 5And R 8Represent hydrogen independently of one another, alkyl or the aryl that replaces arbitrarily, R 6Represent alkyl, haloalkyl or the aryl and the R that replace arbitrarily 7Represent alkyl, haloalkyl or the aryl that replaces arbitrarily in all cases, aralkyl or
Heteroaryl and n represent 0,1 or 2.
Following formula (Ia), (Ib) and (Ic) the preferred structure that replaces of expression
Figure A9419460600191
Figure A9419460600201
Wherein the definition of Ar, W, R and Y is the same.
And be found when formula (II) imidazoles The definition of Ar, W and Y is the same, with the reaction of formula (III) compound,
V-CH 2-R (III) wherein the same and V of the definition of R represents the negatively charged ion leavings group; as chlorine, bromine, iodine, acetoxyl group, tosyl group or methylsulfonyl; if, can obtain formula (I) N-substituted aryl-trifluoromethyl imidazoles in the presence of thinner if the suitably above-mentioned acid acceptor that is reflected at exists down and suitably carries out.
Formula (I) new compound has can make their characteristics as agricultural chemicals.More particularly, they can be used as sterilant, miticide and arthropodicide.
Formula (I) provides the General Definition of the aryl-trifluoromethyl imidazoles of N-replacement.
The preferred definition and the scope that above reach each group in the formula hereinafter described are described as follows: Ar is preferably C 6-C 10Aryl, this group is selected from halogen, nitro, cyano group, C 1-C 12
Alkyl, C 1-C 12Alkylthio, C 1-C 12Alkoxyl group, the divalence dioxy that replaces arbitrarily
Asia-alkyl ,-OCF 2Z ,-S (O) 1CF 2Z and-CF 9R 10Arbitrarily single replace or polysubstituted of identical or different substituting group.W is preferably C 1-C 6Haloalkyl.R is preferably phenyl, and this group is by halogen, cyano group, nitro, C 1-C 6Alkyl,
C 1-C 6Haloalkyl or C 1-C 6Alkoxyl group is single arbitrarily to be replaced to three replacements,
Perhaps be group-OR 1,-SR 1With-N (R 2) COR 3One of.Y be preferably halogen, trifluoromethyl, nitro ,-S (O) nR 6, or C 6-C 10Aryl,
This group be selected from halogen, cyano group, nitro, divalence two oxyalkylenes that replace arbitrarily,
-OCF 2Z ,-S (O) nCFR 9R 10With-CFR 9R 10Identical or different replacement
Base is arbitrarily single to be replaced to three and replaces, in addition, and when Y is positioned on the C-2 position of imidazole ring,
Also represent CN or-CONR 4R 5R 1Be preferably hydrogen, C 1-C 6Alkyl, C 1-C 4Alkoxy-C 1-C 6-
Alkyl, C 1-C 6-haloalkyl, C 3-C 6Cycloalkyl, C 2-C 6
Alkenyl, C 2-C 6Halogenated alkenyl, C 2-C 6Alkynyl group, C 2-C 6
The halo alkynyl group, or be phenyl or benzyl, they are selected from halogen, C separately 1-C 6
Alkyl and C 1-C 6The identical or different substituting group of alkoxyl group is arbitrarily single to be replaced to three and gets
Generation.R 2Be preferably hydrogen, C 1-C 6Alkyl, C 1-C 6Haloalkyl, C 3-C 6
Cycloalkyl, or be phenyl, this phenyl is by halogen, C 1-C 5Alkyl or C 1-C 6
Alkoxyl group is single arbitrarily to be replaced to three replacements.R 3Be preferably (X) mR 7X is preferably 0.M is preferably 0 or 1.R 4And R 5Be preferably hydrogen, C independently of one another 1-C 6Alkyl, or for being selected from halogen
And C 1-C 6The identical or different substituting group of alkyl is single arbitrarily to be replaced to trisubstituted benzene
Base.R 6Be preferably C 1-C 6Alkyl, C 1-C 6Haloalkyl, or be phenyl, this benzene
Base can be selected from halogen, C 1-C 6Alkyl and C 1-C 6Alkoxyl group identical or
The different substituents list replaces to three replacements.R 7Be preferably C 1-C 6Alkyl, C 1-C 6Haloalkyl, or be phenyl or benzyl,
Described phenyl or benzyl separately can be by halogens, C 1-C 6Alkyl, C 1-C 6Alkane
Oxygen base, trifluoromethyl, cyano group or nitro are single arbitrarily to be replaced to three replacements, or the expression pyridine
Base or picolyl, they are selected from halogen, C separately 1-C 6Alkyl and C 1-C 6
The identical or different substituting group of alkoxyl group is single arbitrarily to be replaced to three replacements.R 9And R 10Be preferably hydrogen or halogen independently of one another.Z is preferably hydrogen, halogen or C 1-C 6Haloalkyl.L is preferably 0,1 or 2.N is preferably 0,1 or 2.Ar is preferably phenyl especially, and this phenyl is selected from any of halogen, nitro, cyano group and halogen
The identical or different substituting group of divalence two oxyalkylenes that replace with 1 to 4 carbon atom
Arbitrarily single the replacement to three, replace, or at most by-OCCF 2Z ,-S (O) 1CF 2Z or
-CFR 9R 10Two replace.W is preferably C especially 1-C 4Alkyl, this group can be replaced by fluorine or chlorine.R is preferably group-OR especially 1, SR 1,-N (R 2) COR 7Or-N (R 2) CO 2R 7
One of.Y be preferably especially halogen, trifluoromethyl, nitro ,-S (O) nR 6, or be phenyl,
This phenyl be selected from halogen, cyano group, nitro ,-OCF 2Z ,-S (O) nCFR 9R 10
With-CFR 9R 10Identical or different substituting group arbitrarily single replacement to three replace, in addition,
When Y are positioned on the 2-position of imidazole ring, also represent CN or-CONR 4R 5R 1Be preferably hydrogen especially, or be by 1 to 3 fluorine and/or chlorine atom or by methoxyl group or second
The C that the oxygen base replaces arbitrarily 1-C 4-alkyl, or be C 3-C 6Cycloalkyl,
C 2-C 4Alkenyl, C 2-C 4Alkynyl, C 2-C 4Haloalkenyl group,
C 2-C 4Halo alkynyl, or be phenyl, described phenyl be selected from F, Cl, Br,
C 1-C 4Alkyl and C 1-C 4The identical or different substituting group of alkoxyl group is single arbitrarily
Replacement to three replaces.R 2Be preferably hydrogen, C especially 1-C 4Alkyl, C 1-C 4Haloalkyl, C 3-C 6Ring
Alkyl, or be phenyl, this phenyl can be selected from fluorine, chlorine, bromine, C 1-C 4Alkyl
And C 1-C 4The identical or different substituting group of alkoxyl group is single arbitrarily to be replaced to three replacements.R 4And R 5Be preferably hydrogen, C independently of one another especially 1-C 4Alkyl, or be phenyl, should
Phenyl is selected from fluorine, chlorine, bromine and C 1-C 4The identical or different substituting group of-alkyl
Single arbitrarily the replacement to three replacements.R 6Be preferably methyl especially, it can be selected from the identical or different replacement of fluorine, chlorine and/or bromine
Base is single to be replaced to three replacements.-N (R 2) CO 2R 7In R 7Be preferably C especially 1-C 4Alkyl.-N (R 2) COR 7In R 7Be preferably the C that is randomly replaced especially by halogen 1-C 4
Alkyl, or be phenyl or pyridyl, they are selected from fluorine, chlorine, bromine, C separately 1-C 4
Alkyl and C 1-C 4The identical or different substituting group of alkoxyl group is arbitrarily single to be replaced to three and gets
Generation.R 9And R 10Be preferably hydrogen, fluorine, chlorine or bromine independently of one another especially.Z is preferably hydrogen, fluorine, chlorine or C especially 1-C 4Alkyl, described alkyl by fluorine and/
Or chlorine list replacement or polysubstituted.L is preferably 0 or 1 especially.N is preferably 0,1 or 2 especially.The more special phenyl that is preferably of Ar, described phenyl be selected from fluorine, chlorine, bromine, nitro, cyano group and
Have 1 or 2 carbon atom and by 1 to 4 fluorine and/or chlorine atom replace arbitrarily two
The identical or different substituting group of valency two oxyalkylenes is single arbitrarily to be replaced to three replacements, or at most
Quilt-OCF 2Z ,-S (O) 1CF 2Z or-CFR 9R 10Two replace.The more special CF that is preferably of W 3Or C 2F 5More special formula-the OR that is preferably of R 1,-SR 1,-N (R 2) CO 2R 7Or-NHCOR 7
Group.More special chlorine, bromine, trifluoromethyl, nitro or the phenyl of being preferably of Y, this phenyl is selected from
Fluorine, chlorine, bromine, cyano group, nitro ,-OCF 2Z ,-S (O) nCF 9R 10With
-CFR 9R 10Any Dan Zhisan of identical or different substituting group replace.R 1More special be preferably methyl, ethyl, just-or sec.-propyl or just-, secondary-, exclusive OR
Tert-butyl, they are separately by one to three fluorine and/or chlorine atom or any by methoxyl group
Replace, or be cyclopropyl, cyclopentyl, 2-propenyl, crotyl, 4-chlorine
-crotyl, 2-propynyl or 4-chloro-crotyl, or be by fluorine,
The phenyl that chlorine, bromine, methoxyl group or methyl replace arbitrarily.R 2The more special hydrogen that is preferably, or be methyl, ethyl, just or sec.-propyl or just-, secondary-,
The exclusive OR tert-butyl, they are replaced arbitrarily by one to three fluorine and/or chlorine atom separately,
Or be cyclopropyl or cyclopentyl, or be phenyl, this phenyl is selected from fluorine, chlorine, bromine, first
Any Dan Zhisan of the identical or different substituting group of base and methoxyl group replaces.-N (R 2) CO 2R 7In R 7The more special methyl, ethyl, just-or different third of being preferably
Base or just-, secondary-, the exclusive OR tert-butyl.-NHCOR 7In R 7More special be preferably methyl, ethyl, just-or different-propyl group or just-,
Secondary-, the exclusive OR tert-butyl, they are appointed by 1 to 3 fluorine and/or chlorine atom separately
Meaning replaces, or be phenyl, and this phenyl is selected from fluorine, chlorine, bromine, methyl and methoxyl group
Any list of identical or different substituting group-to three-replacement.R 9And R 10Independently of one another, more special hydrogen, the fluorine or chlorine of being preferably.Z is more special be preferably hydrogen, fluorine, chlorine, difluoromethyl, trifluoromethyl, fluorine chloro methyl or
Formula-CHFCF 3Base.L is more special to be preferably 0.N is more special to be preferably 0 or 1.
The above-mentioned definition or the scope of each group of mentioning in that generally mentioned or its preferable range can make up to each other mutually, i.e. any combination between specified range and preferable range also is possible.They are applicable to final product, equally also are applicable to precursor and intermediate.
The preferred general formula of the present invention (I) compound comprises that above-mentioned preferred definition makes up those compounds that obtain.
Particularly preferred general formula of the present invention (I) compound comprises the combination of above-mentioned special preferred definition and those compounds of obtaining.
More particularly preferred general formula of the present invention (I) compound comprises the combination of above-mentioned more special preferred definition and those compounds of obtaining.
For example, if 2-trifluoromethyl-4,5-[two (4-fluorophenyls)] imidazoles and chloromethyl ethyl ether be used as raw material, and the then available following reaction formula of the reaction process of the inventive method is represented:
Figure A9419460600261
For example, if 2-trifluoromethyl-4 (5)-chloro-5 (4)-(4-chloro-phenyl-) imidazoles and acetyl-o-methyl ethanamide are used as starting raw material, the then available following reaction formula of the reaction process of the inventive method is represented:
Formula (II) provides the General Definition of imidazoles, and this compound is as the starting raw material that carries out the inventive method.In the formula (II), on behalf of those, Ar, W and Y preferably for these substituting groups be the group of mentioning already aspect the description of preferred formula (I) compound.Wherein some formula (II) compound is new.
In general, preparation 4 hereinafter described, the method for the formula of the asymmetric replacement in 5-position (II) imidazoles produces the isomer mixture of substituting group on 4-and 5-position usually.
Therefore, if suitable, by the prepared formula of the inventive method (I) compound with the isomer mixture form obtain (referring to, Adv.Heterocycl.Chem.1980,27,241).In general, these isomer mixtures can be separated by chromatography or fractional crystallization, chromatography such as column chromatography, in or high pressure liquid chromatography.
According to definition and their positions in molecule of substituent A r and Y,, there is following preparation variant method for formula (II) starting compound.
The following formula (IIa) that is used as enforcement the inventive method starting raw material is known and/or can be by obtaining (referring to US 4 314 844 with the similar method of currently known methods; J.Med.Chem.1975,18,895; EP 0 283 173).
Figure A9419460600271
Wherein the definition of Ar, W and Y is the same.
Formula (IIa-a) 2-aryl-4,5-two (trifluoromethyl) imidazoles is a new compound: Wherein the definition of any aryl that replaces of Ar representative and W is the same, and above-claimed cpd can be used as the starting raw material of implementing the inventive method.
Formula (IIa-a) imidazoles prepares as follows:
Make formula (IV) benzamidine
Figure A9419460600282
Wherein the definition of Ar is the same, reacts with the formula V compound
Figure A9419460600283
Wherein the definition of W is the same, if the suitably above-mentioned thinner that is reflected at exists down and carries out, and if in the presence of alkali and suitable formula (VIa) that cyclisation generated in the presence of thinner or (VIb) compound:
Figure A9419460600291
Figure A9419460600292
Wherein the definition of Ar and W is the same.
For example, if benzamidine and 2,3-two chloro-1,1,1,4,4,4-hexafluoro-2-butylene is used as above-mentioned preparation method's raw material, and then reaction process can be represented with following reaction formula:
Figure A9419460600293
The preparation method of formula (IIa-a) compound is characterised in that: in the first step, formula (IV) benzamidine and the reaction of formula V compound, if suitably in the presence of thinner, carry out, subsequently with the formula (VIa) that generated if or (VIb) compound in second step in the presence of the alkali and suitably in the presence of thinner, carry out cyclisation.The thinner that is suitable for the use of the aforesaid method the first step is inert organic solvents.They preferably include hydrocarbon, as benzene,toluene,xylene, and ether, as dibutyl ether, t-butyl methyl ether, tetrahydrofuran (THF), diox comprise polar solvent, in addition as methyl-sulphoxide, acetonitrile, tetramethylene sulfone, dimethyl formamide and N-Methyl pyrrolidone.
When carrying out the first step, temperature of reaction can change in wide relatively scope.In general, the first step is carried out under the temperature between preferred 20 ℃ to 100 ℃ at 0 ℃ to 150 ℃.
When carrying out the first step, the usually formula (IV) of mol ratio such as use and (V) reactant also can be used excessive formula V reactant.
Usually reaction is under atmospheric pressure to carry out.
Be suitable for mentioned thinner in the aforesaid method the same the first step of thinner in second step.
Second step of aforesaid method is to carry out in the presence of alkali.Spendable alkali comprises all conventional proton acceptors.Can preferably use following alkali: the oxide compound of basic metal and alkaline-earth metal, oxyhydroxide and carbonate, as magnesium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, yellow soda ash, salt of wormwood and lime carbonate.All these alkali also can use in the presence of phase-transfer catalyst, these catalyzer such as chlorination triethyl benzyl amine, bromination four butylamine or 18-hat-6, other alkali that can be used has the amide and the hydride of basic metal and alkaline-earth metal, as ammonification sodium, sodium hydride and hydrolith, also has alkali metal alcoholates in addition, as sodium methylate, sodium ethylate and potassium tert.-butoxide.
When carrying out for second step, temperature of reaction can change in the scope of relative broad.Common second step carries out under the temperature between preferred 20 ℃ to 120 ℃ at 0 ℃ to 150 ℃.
Used alkali uses with equimolar amount or uses with the excessive amount of 5 times of as many as.
In general, second step under atmospheric pressure carried out.
Formula (IIa-a) compound has constituted one of purpose of the present invention, and they have insecticidal property.
Formula (IIb) imidazoles
Figure A9419460600311
Wherein the definition of Ar, W and Y is the same, be known and/or can make by the method that is similar to currently known methods (referring to, for example, JP02 262 560), they can be used as the starting raw material of implementing the inventive method.
Formula (IIb-a) imidazoles is a new compound:
Figure A9419460600312
Ar wherein 1The aryl that representative replaces, suitable substituents is seen described in the Ar, and Y 1Represent halogen, nitro or group-S (O) nR 6, R wherein 6It is the same with the definition of n,
And the definition of W is the same.
Formula (IIb-a) imidazoles makes by making formula (VII) compound carry out following reaction
Figure A9419460600321
Ar wherein 1The same with the definition of W, a) at-20 ℃ to 150 ℃, under the temperature between preferred 0 ℃ to 100 ℃, if suitably in the presence of thinner such as acetate, react with nitrating agent, the mixture of described nitrating agent such as concentrated nitric acid and the vitriol oil, or b) at-20 ℃ to+100 ℃, under the temperature between preferred 0 ℃ to 50 ℃, if suitably in the presence of thinner, react with formula (XIII) sulfenyl chlorine:
R 6SCl (XIII) is R wherein 6Definition the same, wherein said thinner such as methylene dichloride, trichloromethane, tetrachloromethane, ethylene dichloride, ether or tetrahydrofuran (THF), and, if suitably, subsequently with formula (IIb-b) compound that is generated:
Figure A9419460600322
R wherein 6, W and Ar 1Definition the same, with oxygenant in-20 ℃ to+100 ℃, under the temperature between preferred 0 ℃ to 25 ℃, and if suitably in the presence of thinner, react, wherein said oxygenant as-the chlorine peroxybenzoic acid, peroxy-disulfuric acid hydrogen potassium or H 2O 2Described rare solvent such as toluene, chloroform, tetrahydrofuran (THF), ethanol or water; Or c) in-10 ℃ to+100 ℃, under the temperature between preferred 0 ℃ to 50 ℃, if suitably in the presence of thinner, react wherein said thinner such as acetate, trichloromethane, tetrachloromethane, ether, tetrahydrofuran (THF) or water with halogenating agent such as bromine or chlorine.
Formula (IIb-c) compound
Figure A9419460600331
Wherein the definition of Ar and W is the same, and Y 2The aryl that representative replaces arbitrarily, suitable substituting group sees that aryl moiety is described among the above-mentioned Y, is known and/or can makes by the method that is similar to currently known methods (referring to No. 2 155 558, German Patent prospectus; J.Med.Chem.1984,17,1182).
Formula (IIc) imidazoles
Figure A9419460600332
Wherein the definition of Ar, W and Y is the same, is known and/or can makes by the method that is similar to currently known methods (referring to No. 2,155,558, German Patent prospectus; J.Heterocycl.Chem.1973,10,697), they can be used as the starting raw material of implementing the inventive method.
Formula (IIc-a) imidazoles is a new compound:
Figure A9419460600341
Wherein the definition of Ar and W is the same, Y 3Represent halogen, cyano group or group-CONR 4R 5, R wherein 4And R 5Definition the same.
New formula (IIc-a) imidazoles can make by following reaction: the first step makes formula (VIII) imidazoles Wherein the definition of Ar and W is the same, with halogenating agent such as chlorine or bromine in-10 ℃ to+150 ℃, under the temperature between preferred 20 ℃ to 120 ℃, if suitably in the presence of thinner such as acetate, trichloromethane or dimethyl formamide, react, perhaps, if suitably, use hydrochloric acid or gaseous hydrogen chloride in 0 ℃ to 150 ℃, under preferred 80 ℃ to the 150 ℃ temperature, if suitably in the presence of thinner such as acetate or dimethyl formamide, bromine is exchanged into chlorine, second step, if suitably, with formula (IIc-b) imidazoles that is generated:
Figure A9419460600351
Wherein the same and Hal of the definition of Ar and W represents halogen, and particularly chlorine or bromine reacts (referring to JP 0 399 065) with CuCN and KCN mixture; Perhaps
With formula (VIII) compound
Figure A9419460600352
Wherein the definition of Ar and W is the same, at first reacts with formula (XVIII) compound:
Pg-Hal (XVIII) wherein Pg represents protecting group, as-CH 2-O-CH 3,-CH 2-O-C 2H 5,-SO 2N (CH 3) 2
Or (trimethyl silyl) ethoxymethyl and Hal represent chlorine or bromine,
If suitably, above-mentioned reaction is in the presence of thinner such as acetonitrile, and if suitably, in the presence of alkali such as salt of wormwood, carry out, with formula (XIV) compound that is generated
Figure A9419460600361
Wherein the definition of Ar, W and Pg is the same, and the metallizing thing is as alkyl lithium compounds, particularly n-Butyl Lithium, reaction in the presence of thinner such as normal hexane, then with N, dibasic carboxamides derivatives of N-such as N, dinethylformamide, if suitably react at thinner such as tetrahydrofuran (THF) existence (for example, referring to J.Org.Chem.45,4038,1980), then with formula (XV) compound that is generated:
Figure A9419460600362
Wherein the definition of Ar, W and Pg is the same, with azanol reaction, if if suitably carry out, handles resulting formula (XVI) oxime with dewatering agent such as acetic anhydride or phosphoryl chloride in the presence of thinner and suitably in the presence of alkali such as pyridine:
Figure A9419460600363
Wherein the definition of Ar, W and Pg is the same, last formula (XVII) compound that heating is generated in the presence of sour example hydrochloric acid: Wherein the definition of Ar, W and Pg is the same, and the formula that hydrolysis generated (IIc-c) imidazoles
Figure A9419460600372
Wherein the definition of Ar and W is the same, if suitably carry out in the presence of acid, utilizes thionyl chloride that following formula (IIc-d) compound that generates is changed into corresponding acyl chlorides:
Figure A9419460600373
Wherein the definition of Ar and W is the same, and these acyl chlorides and formula (IX) amine are reacted:
HNR 4R 5(IX) R wherein 4And R 5Definition the same, if if suitably in the presence of thinner and suitably, in the presence of acid acceptor, carry out (referring to J.March, Advanced Organic Chemistry, Third Edition, Wiley, New York 1985, pp.788,388,370).
Formula (IIc-e) imidazoles is new compound and also is one of theme of the present invention: Ar wherein 1The same with the definition of W.
Formula (IIc-e) but new imidazoles through type (X) compound:
Figure A9419460600382
Ar wherein 1The same with the definition of W, contract an ethanol in the presence of ammonium acetate with following formula (XI) trifluoro acetaldehyde, and if suitably in the presence of thinner, react and make (referring to the German Patent prospectus: 2 155 No. 558; J.Heterocycl.Chem., 1973,10,697):
Figure A9419460600391
Formula (IIc-f) imidazoles also is a new compound:
Figure A9419460600392
Ar wherein 1The same with the definition of W, and Ar 2The aryl that representative replaces arbitrarily, suitable substituting group are seen upward described in the Ar.
The new imidazoles of formula (IIc-f) is by making formula (X) compound: Ar wherein 1The same with the definition of W, with formula (XII) aldehyde
Ar 2-CHO (XII) is Ar wherein 2Definition the same, in the presence of ammonium acetate, and if suitably in the presence of thinner prepared in reaction (referring to No. 2 155 558, German Patent prospectus; J.Heterocycl.Chem., 1973,10,697).
New formula (IIc-a) to (IIc-f) imidazoles itself has insecticidal properties.
Formula (IV) benzamidine is known and/or can be by the method preparation (referring to Patai, " The Chemistry of Amidines and Imidates ", wiley, New York, 1975) that is similar to currently known methods.
The formula V compound is known (for example referring to US 3,965,201).
Formula (VII) 2-haloalkyl-4 (5)-Aryimidazole is known in some cases and/or can be by the method preparation (referring to JP 02 262 560) that is similar to currently known methods.
Formula (VIII) 4 (5)-aryl-5 (4) but-haloalkyl imidazoles through type (X) compound and formaldehyde equivalent such as Paraformaldehyde 96 or urotropine prepared in reaction (referring to J.Org.Chem, 1938,2,319) in the presence of ammonium acetate.
Formula (X) compound is known in some cases and/or can be by the method preparation that is similar to currently known methods (for example, referring to J.Org.Chem, 1988,53,129).
Formula (IX) amine, formula (XI) hemiacetal, formula (XII) aldehyde, formula (XIII) sulfenyl chlorine and formula (XVIII) compound are generally the known compound of organic chemistry filed.
Formula (III) compound that can be used as enforcement the inventive method initial substance is known and/or can be similar to currently known methods preparation (referring to DE-2119515, US 5130328).
The method of preparation formula of the present invention (I) new compound preferably uses thinner to carry out.In fact suitable diluent comprises all inert organic solvents.They preferably include aliphatic series and any halogenated hydro carbons of aromatics, as pentane, and hexane, heptane, hexanaphthene, sherwood oil, gasoline, ligroin, benzene, toluene, dimethylbenzene, methylene dichloride, ethylene chloride, chloroform, tetracol phenixin, chlorobenzene and neighbour-dichlorobenzene, ether is as ether and dibutyl ether, glycol dimethyl ether and diglyme, tetrahydrofuran (THF) be with diox, ketone such as acetone, methylethylketone, methyl isopropyl Ketone and methyl iso-butyl ketone (MIBK), ester, as methyl acetate and ethyl acetate, nitrile such as acetonitrile and propionitrile, acid amides such as dimethyl formamide, N,N-DIMETHYLACETAMIDE and N-Methyl pyrrolidone, and methyl-sulphoxide, tetramethylene sulfone and hexamethylphosphoramide.
The acid acceptor that can use in the methods of the invention comprises that all routines are used for the acid binding agent of this type of reaction.Following part is suitable especially: alkalimetal hydride and alkaline earth metal hydride, as lithium hydride, sodium hydride, potassium hydride KH and hydrolith, alkali metal hydroxide and alkaline earth metal hydroxides, as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkaline carbonate, alkali metal hydrocarbonate, alkaline earth metal carbonate and alkali metal bicarbonates.As yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus and lime carbonate, alkali metal acetate, as sodium acetate and potassium acetate, alkali metal alcoholates such as sodium tert-butoxide and potassium tert.-butoxide comprise basic nitrogen compound in addition, as Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine, Diisopropylamine, dicyclohexyl amine, diisopropylethylamine, dicyclohexyl ethamine, N, N-dimethyl benzylamine, N, accelerine, pyridine, the 2-methyl-, the 3-methyl-, the 4-methyl-, 2, the 4-dimethyl-, 2, the 6-dimethyl-, the 2-ethyl-, the 4-ethyl-and 5-ethyl-2-methyl-pyridine, 1,5-diazabicylo [4,3,0] ninth of the ten Heavenly Stems-5-alkene (DBN), 1,8-diazabicylo [5,4,0]-+-carbon-7-alkene (DBU) and 1,4-diazabicylo [2,2,2]-octane (DABCO).
When implementing the inventive method, temperature of reaction can be in the interior variation of wide relatively scope.In general, aforesaid method is at 0 ℃ to 100 ℃, carries out under preferred 10 ℃ to the 80 ℃ scope.
In general, the inventive method is under atmospheric pressure to carry out.Yet, also may under the pressure that raises or reduce, carry out.
When implementing the inventive method, needed in all cases raw material generally uses with about equimolar amount, then, also one of two kinds of used components can be used with big excessive amount in all cases.In general, reaction is to carry out in the presence of acid acceptor in suitable diluent, and with reaction mixture stirred for several hour under every kind of needed temperature of situation.Treatment step in the inventive method all carries out (referring to preparation embodiment) according to a conventional method under every situation.
Formula of the present invention (I) compound can be used to kill pests.Insect is meant undesirable animal pest, particularly insect and mite, their harm plant or superior beings.
Active compound of the present invention is suitable for the animal pest that goes out; preferred arthropods; especially on agricultural; forest; the insect that is run in the protection aspect of storage product and material and the sanitation and health-care field and the animal of spider steel, and they have the plant resistance of good thing and warm-blooded animal are had suitable toxicity.The compounds of this invention can effectively be prevented and treated common sensitivity and pest species with resistance, and all or some etap of these insects are all had activity.Above-mentioned insect comprises:
Isoptera, for example damp worm, pillworm and armadillidum vulgare.
The Diplopoda order is for example had a zebra land.
The chilopoda order for example, is planted in food fruit DIWUGONG and common house centipede belong to.
Flat shoulder detailed outline, for example, clean symphilid.
Thysanura, for example, silverfiss.
Collembola, for example, tool thorn springtail.
Orthoptera, for example, oriental cockroach, periplaneta americana, the Ma Dela blattaria, Groton bug is planted in the acheta domestica, Gryllotalpa spp, and the Asia migratory locusts are very planted grasshopper and desert locust.
Dermaptera, for example, European earwig.
Isoptera, for example, Cryptotermes.
Anoplura, for example, body louse, blind lice belongs to, and the jaw lice belongs to.
Mallophaga, for example, Trichodectes and Damalinia.
Thysanoptera, for example, greenhouse Hercinothrips spp and cotton thrips.
Heteroptera, for example, brown scutteleerid belongs to, and red stinkbug belongs to, and beet is intended lace bug, and bedbug is planted in phodnius prolixus and triatoma sanguisuga belong to.
Hemiptera, for example, wild cabbage aleyrodid, sweet potato whitefly, greenhouse whitefly, cotten aphid, brevicoryne brassicae tea sugarcane conceals knurl aphid, aphis fabae, apple aphid, eriosoma lanigerum, mealy plum aphid, grain aphid, tumor aphid genus, hops wart volume aphid, wooden paddy Rhopalosiphum spp, grape phylloxera is planted in the knurl cotten aphid belongs to, and plants Euscelis bilobatus in leafhopper belongs to, rice green leafhopper, ceroplastes brown helmet, tea helmet a red-spotted lizard (Saissetia oleae), small brown-back rice plant-hopper, Nilaparvata lugen (brown planthopper), carefully round a red-spotted lizard, Folium seu Cortex Nerii circle a red-spotted lizard is planted in mealybug and the Psylla spp.
Lepidopteran, for example, pink bollworm, loose looper, winter moth, the thin moth of apple, cherry ermine moth, small cabbage moth, tent caterpillar, pornography and drug moth, Euproctis, cotton shot hole of leaf lyonetid, plant in the tangerine lyonetid, Agrotis, plant Feltia SPP. in cutworm belongs to, Egyptian golden steel bores, and plant beet armyworm, lopper worm in the Plutella night, small noctuid, prodenia litura, mythimna separata belongs to, cabbage looper, plant in the stupid moth of apple, Yponomeuta, plant Pyrausta nubilalis (Hubern). in snout moth's larva belongs to, Mediterranean flour moth, greater wax moth, bag casemaking clothes moth, etting moth, brown oecophorid, the yellow volume of flax moth, tool net leaf roller, choristoneura fumigerana, grape codling moth (Clysia ambiguella), the green volume of Homonq magnanima and oak (leaf) moth.
Coleoptera, for example, furniture is surreptitiously stupid, Rhizopertha dominica, two acanthoscelides obtectus, North America house longhorn beetle, the purple flea beetle of alder, colorado potato bug, the horseradish ape is chrysomelid, plants the blue flea beetle of rape, mexican bean ladybird in the chrysomelid genus, Atomaria SPP. plants in the saw-toothed grain beetle Anthonomus spp belongs to, and plants in the Sitophilus, black vine weevil, banana weevil borers base, wild cabbage pod weevil, alfalfa weevil, khapra beetle belongs to, and plants in the spot khapra beetle; Anthrenus SPP., the moth-eaten genus of fur, the stupid genus of powder, pollen beetle, Ptinus SPP., golden yellow ptinid is planted the bloom first in the wheat ptinid, Tribolium, plant in click beetle belongs to, gold month worm first, Melontha melolontha, June chafer and Costelytra zealandica.
Hymenoptera for example, is planted in Ye Feng belongs to, and plants in the fertile leaf peak belongs to, and plants in the field ant belongs to, and plants in kitchen ant and honeybee belong to.
Diptera for example, is planted anopheles in the Aedes, culex is planted in the drosophila yellow gorilla, Musca, plants in the abdomen stable fly belongs to, the calliphora erythrocephala lucilia sericata is planted in belonging to, and plants in the golden fly, and cuterbrid belongs to several, plants in the Gasterophilus, Hyppobosca SPP plants in stable fly belongs to, and plants in the Oestrus, Hypoderma, the gadfly is planted in belonging to, and Tannia SPP. spends round march fly, auspicious tribute fly, the wheat fly is planted in belonging to, kmangold fly, Mediterranean fruitfly, dacus oleae and European daddy-longlegs.
Siphonaptera, for example, Xenopsyllacheopis and leaf flea belong to several.
The Arachnida order, for example, scorpion and black widow.
Acarina, for example, Acarus siro is planted in latent beak tick belongs to, in belonging to, the beak tick plants Dermanyssus gallinae, tea sugarcane goitre mite, the tangerine rust mite that rues, plant in the Boophilus, plant in the Rh, plant in the Amblyomma, plant in the Hyalomma, plant in hard tick belongs to, plant the skin Psoroptes in the Psoroptes, itch mite is planted in belonging to, and plants Bryobia praetiosa in line wax belongs to, the pawl mite is planted in belonging to, and plants HemitarsonemusSPP in tetranychus telarius belongs to.
Be provided as the usefulness of sterilant and miticide, active compound of the present invention can exist wherein said activeconstituents such as sterilant, attractive substance, apholate, miticide, nematocides, bactericide, mycocide, growth regulator or weedicide with its dosage form available on the market and with the use formulation by these preparations and the prepared form of mixtures of other activeconstituents.For example sterilant comprises phosphoric acid ester, carbamate, carboxylicesters, chlorinated hydrocarbon, phenylurea, by the material of microorganisms, or the like.
The example of particularly preferred component comprises in the mixture: mycocide:
2-aminobutane: 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6 '-two bromo-2-methyl-4 '-trifluoromethoxy-4 '-Trifluoromethyl-1,3-thiadiazoles-5-formylaniline; 2,6-two chloro-N-(4-trifluoromethyl benzyl) benzamide; (E)-2-methoxyimino-N-methyl-2-(2-phenoxy phenyl)-ethanamide; Oxine vitriol; (E)-2-{2-[6-(2-cyano-benzene oxygen)-pyrimidine-4-base oxygen base]-phenyl }-the 3-methoxy-methyl acrylate; (E)-methoxyimino [α-(neighbour-tolyloxy)-o-tolyl] methyl acetate; 2-phenylphenol (OPP): aldimorph, ampropylfos, anilazine, ammonia health azoles, the spirit of withering of benodanil, sulphur, F-1991, Niagara 9044, biphenyl, bitertanol, miewensu, bromuconazole, the phonetic bacterium spirit of sulphur, buthiobate, calcium polysulfide, Difolatan, Vancide 89, derosal, the spirit of green bristlegrass rust, chinomethionate, chloroneb, trichloronitromethane, m-tetrachlorophthalodinitrile, chlozolinate, thia record, cymoxanil, cyproconazole, cyprofuram, dichlorophen, diclobutrazol, diclofluanid, diclomezin, dicloran, diethofencarb, Mildex, Milcurb, dimethomorph, diniconazole, dinocap, pentanoic, dipyri-thion, ditalimfos, Delan, dodine, drazoxolon, Hinosan, epoxyconazole, Milstem, Truban, fenarimol, fenbuconazole, methuroxam, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentinacetate, fentin hydroxide, Karbam Black, ferimzone, fluazinam, fludioxonil, fluorine bacterium peace, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, Phaltan, fosetyl-alumirnum, phthalide, fuberidazole, Furalaxyl, furmecyclox, Guanoctine, Perchlorobenzene, hexaconazole, hymexazol, IMAZALIL, imibenconazole, iminoctadine, iprobenfos, different third is fixed, Fujione, kasugamycin, copper agent is as copper hydroxide, copper naphthenate, Cupravit, blue vitriol, cupric oxide, quinolinone and Bordeaux mixture, the copper-manganese mixture, mancozeb, Dai Senmeng, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, the first methuroxam, Carbatene, metsulfovax, myclobutanil, Sankel, different third disappears, the spirit of ring bacterium, ofurace, oxadixyl, oxamocarb, the spirit of oxidation green bristlegrass rust, perfurazoate, penconazole, pencycuron, phosdiphen, phthalide, myprozine, pipron, polycarbamate, Polyoxin, thiabendazole, Prochloraz, sterilization profit, hundred dimension spirits, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozene, sulfur flour and sulphur preparation, tebuconazole, tecloftalam, tecnazene, tetraconazole, Apl-Luster, thicyofen, thiophanate methyl, thiram, tolclophos-methyl, tolylfluanid, cycloheximide triazole, Triabimeno I, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, validamycin-A, vinclozolin, zineb, ziram.Bactericide:
Bronopol, dichlorophen, N-Serve, Sankel, kasugamycin, octhilinone, furancarboxylic acid, terramycin, thiabendazole, Streptomycin sulphate, tecloftalam, blue vitriol and other copper agent.Insecticide/miticide/nematocides:
Abamectin, AC 3,003 630, Ortho 12420, kill mite chrysanthemum ester, alanycarb, aldicarb, alphacypermethrin, U-36059, avermectin, AZ 60541, azadirachtin, R-1582 A, azinphos M, azoles ring tin, Bacillus thuringiensis, thuringiensis ， Evil worm prestige, benfuracarb, bensultap, β-hundred controls chrysanthemum ester, bifenthrin, BPMC, brofenprox, bromofos A, bufencarb, buprofezin, fourth fork prestige, butylpyridaben, cadusafos, SevinCarbaryl, carbofuran, carbophenothion, carbosulfan, Padan, CGA157 419, and CGA 184 699, chloethocarb, chlorethoxyfos, Zaprawa enolofos, ohlorfluazuron, chlormephos, Chlorpyrifos 94, chlorpyrifos M, cis-resmethrin, lambda-cyhalothrin, clofentezine, cynock kills snout moth's larva chrysanthemum ester, hundred control chrysanthemum ester, cyfloxylate, cyhexatin, Cypermethrin, cyromazine, Deltamethrin, methyl 1, one zero five nine, the thiol formula isomer of methyl 1, diafenthiuron, diazinon, dichlofenthion, SD-1750, dicliphos, Carbicron, Nialate, diflubenzuron Rogor, dimethylvinphos, dioxathion, thiodemeton, Hinosan, emamectin, esfenvalerate, benzene worm prestige, Nialate, ether chrysanthemum ester, ethoprop, etrimphos, Nemacur, fenazaquin, fenbutatin oxide, Sumithion, fenobucarb, fenothiocarb, fenoxycarb, Fenvalerate, fenpyrad, fenpyroximate, Tiguvon, fenvalerate, fipronil, fluazinam, flucycloxuron, fluoro-Cyano chrysanthemate, flufenoxuron, flufenprox, taufluvalinate, fohophos, the peace fruit, fosthiazate, fubfenprox, furathiocarb, phenyl-hexachloride, heptan worm phosphorus, hexaflumuron, hexythiazox, imidacloprid, iprobenfos, isazophos, propylamine phosphorus, isoprocarb ， karphos, ivermectin, cyhalothrin, lufenuron, Malathion, mecarbam, Phosdrin, mesulfenphos, Halizan, methacrifos, acephatemet, methidathion, metmercapturon, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin, naled, NC 184, NI 25, nitenpyram, omethoate, thioxamyl, oxydemeton methyl, oxydeprofos, one six zero five, methyl 1, permethrin, Tsidial, phorate, zolone, R-1504, phosphamidon, phoxim, Aphox, pirimiphosmethyl, pirimiphos A, bromine third phosphorus, promecarb, Kayaphos, Propoxur, Toyodan, prothoate, pymetrozin, pyrachlophos, Ofunack, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen ， quinalphos, RH 5992, salithion, sebufos, silafluofen, dithione, Toyodan, tebufenozid, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, terbam, Terbufos, tetrachlorvinphos, thiafenox, thiodicarb, special ammonia fork prestige, thiometon, ethyl pyrazinyl phosphorothioate, thuringiensin, tralomethrin, triarathen, triazophos, triazuron, Trichlorphon, triflumuron, trimethacarb, vamidothion, Cosban, xylylcarb, YI 5301/5302, zetamethrin.Weedicide:
Anilide class for example is as diflufenican and Stam F-34: aryl carboxylic acid such as morpholine acid dichloride picoline, dicamba 98 and picloram; The aryloxy paraffinic acid as, 2,4-drips, 2,4-Embutox, 2,4-DP, fluoroxypyr, 2 first, 4 chlorine, Vi par and triclopyr; Aryloxy-phenoxy group-alkanoates such as chloroformate grass, ethoxy phenol propionic acid (fenoxaprop-ethyl), fluazifop-butyl, haloxyfop-methyl, and quizalofop-ethyl; Azinones such as chloridazon and monometflurazone; Carbamate such as Y 3, different phenmedipham, phenmedipham and propham: chloracetanilide such as alachlor, mowing amine, Machete, metazachlor, the third careless amine, pretilachlor and propachlor; The careless amine of N-acyl group dinitraniline such as Huang, pendimethalin and trifluralin: diphenyl ether such as acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and Oxyfluorfen; Urea such as chlorotoluron, Diuron Tech, fluometuron, isoproturon, methoxydiuron and methabenzthiazuron; Hydroxyl amine such as witheredly reach clethodim, cycloxydim, sethoxydim and tralkoxydim extremely; Imidazolone such as imazethapyr, imazamethabenz, imazapyr and imazaquin: nitrile such as bromoxynil, Niagara 5006 and ioxynil; Acetic oxide amine (oxyacetamides) is as mefenacet; Sulfonylurea such as amino sulphur urea, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; Thiocarbamate such as butylate, cycloate, di_allate, Eptam, esprocarb, Hydram, prosulfocarb, thiobencarb and weeds fear; Two pyridine class such as G-30027s, bladex, simazine, simetryn, terbutryn and terbuthylazine; Triazone as six piperazines with, benzene piperazine grass and sencorex: other is as amerol, benfuresate, bentazon, cinmethylin, clomazone, clopyralid, the benzene enemy is fast, dithiopyr, ethofumesate, fluorochloridone, glufosihate, glyphosate, isoxaben reaches grass and ends, quinchlorac, quinmerac, sulfosate and tridiphane.
Active compound of the present invention can be further exists with its dosage form available on the market and with the use formulation of the form of mixtures made by these preparations and synergistic agent.Synergistic agent is meant the compound of the effect of energy enhanced activity compound, and the synergistic agent that is added itself might not have activity.
Can in relative broad range, change by the active quantities that can obtain on the market in the made use formulation of preparation.Using the concentration of active compound in the formulation is 0.0000001 to 95% (weight) active compound, preferably between 0.0001 to 1% (weight).
Active compound of the present invention can be fit to the usual manner of above-mentioned use formulation and use.
The compounds of this invention also is particularly suitable for handling plant and regeneration propagulum, as cereal, and corn, plant etc. and seed, or handle onion, nursery sapling etc.
When being used to prevent and treat the insect pest of health and pest and storage article, active compound is to have superior residual action and the alkalescence of lime base material is had good stability and is celebrated to wooden and earth.
Active compound of the present invention can be applied through its dosage form, or uses with the use dosage form of making by the above-mentioned preparation of further dilution, as used solution, and suspension, emulsion, pulvis, paste and granula.They by as sprinkle and to water, spray, spray or the usual manner that broadcasts sowing dispenser is used.
Active compound of the present invention can be used before plant germination or after germinateing.
They also can be admixed in the soil before sowing.
The amount of used active compound can change in wide relatively scope, and this depends on the degree of useful effect basically.In general, formulation rate is per hectare soil area 10g to a 10kg active compound, preferred 50g to 5kg/ha.
Be the preparation agricultural chemicals, according to its special physics and/or chemical property, active compound of the present invention can be converted to conventional formulation: as solution, emulsion, suspension, pulvis, foaming agent, paste, granula, aerosol, be impregnated with the natural or synthetic material of active compound, tiny capsules agent in polymkeric substance and be coated with the tiny capsules of stain in the composition at seed, and the formulation of together using with combustion equipment, as fumigation tube, fumigation tank, stifling coil (fumigating coils) etc., and micro-cold spray agent and micro-thermal spray agent (Ulv Cold mist and Warm mistformulations).
These preparations are pressed the currently known methods preparation, for example pass through with active compound and filler, promptly with liquid solvent, add the liquefied gas of depressing, and/or the solid carrier mixing, and randomly use tensio-active agent, be floating agent and/or dispersion agent, and/or foam agent and preparing.Under the situation that makes water as filler, organic solvent also can be used as solubility promoter.As for liquid solvent, suitable mainly comprises: aromatic hydrocarbons, as dimethylbenzene, toluene or alkylnaphthalene, chlorinated aromatics or chlorination aliphatic hydrocrbon are as chlorobenzene, vinylchlorid or methylene dichloride, aliphatic hydrocrbon such as hexanaphthene or paraffin, for example mineral oil fractions, alcohol is as butanols or glycol and their ether and ester, ketone such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK) or pimelinketone, intensive polar solvent such as dimethyl formamide and methyl-sulphoxide, and water; Liquefied gas extender or carrier are meant that room temperature and normal atmosphere are gasiform liquid down, for example, and aerosol propellants such as halohydrocarbon and butane, propane, nitrogen and carbonic acid gas; As for solid carrier, suitable comprises: ground natural mineral matter for example resembles kaolin, clay, talcum, chalk, quartzy, U.S.'s atlapulgite, polynite or diatomite, and ground synthetic mineral material, as the high dispersing silica, alumina and silicate: as for the granula solid carrier, suitable comprises: the classification natural rock such as the calcite that for example pulverize, marble, float stone, sepiolite and rhombspar, and inorganic and organic powder particles of synthetic and organic materials particle, these organic materialss such as sawdust, Exocarpium cocois (Cocos nucifera L), corn cob, tobacco rods; As for emulsification and/or foam agent, suitable comprises: for example, nonionic and anionic emulsifier are as polyoxyethylene fatty acid ester, the polyoxyethylene aliphatic alcohol ether, for example, the alkaryl polyglycol ether, alkylsulfonate, alkyl-sulphate, arylsulphonate and protein hydrolysate; As for dispersion agent, suitable has: for example lignin-sulfite waste lye and methylcellulose gum.
Can use tackiness agent in the preparation, as carboxymethyl cellulose and powdery, granular or the natural and synthetic polymer of glue lactous, as Sudan Gum-arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipid, as kephalin and Yelkin TTS, and synthetic phospholipid.Other additive can be mineral oil and vegetables oil.
Allow to use tinting material such as mineral dye, ferric oxide for example, titanium oxide and Prussian orchid, and organic dye, as alizarine dyestuff, azoic dyestuff and metal phthalocyanine dyestuff, and trace nutrition such as iron, magnesium, boron, copper, cobalt, the salt of molybdenum and zinc.
Preparation generally contains 0.1 to 95% (weight) active compound, preferred 0.5 to 90%.
More preferably in the present composition except that comprising at least a general formula (I) compound, and if suitably, except that extender and auxiliary, also comprise at least a tensio-active agent.
Although warm-blooded animal is had suitable toxicity, but active compound of the present invention also is suitable for killing domestic animal and breeding domestic animal, and zoo animal, laboratory animal, the animal pest that is occurred in animal rearing of test animal and pet and the cattle breeding process (outer-and endoparasite), as save the amine animal, preferred insect and spider guiding principle animal (epizoon).They are all effective to all etap or some etap of insect, and can effectively prevent and treat the pest species with resistance and common susceptibility.Kill pests be intended that preventing disease and propagation thereof, death and degraded performance (decreasing performance) are (for example at meat, milk, wool, leather, in the production process of egg), the result is by using active compound might make animal rearing become more economical and simpler, fully may perhaps becoming in some field.These insects comprise:
The Anoplura order is planted in for example blind lice belongs to, and plants in the jaw lice belongs to, and plants in the Solenopsis, plants in the Cuclotogaster, plants in the Ptinus.
Mallophaga, for example, Trimenopon SPP, Menopon SPP, EomenacanthusSPP plants in feather belongs to, and plants DamalinaSPP, Bovicola SPP in the Trichodectes SPP, Felicola.
Diptera for example, is planted in the Chrysops, plant in the Gadfly, plant HydrotaeaSPP in the Musca, plant in the Muscina, Haematobosca SPP plants in the blood fly belongs to, plant in the Genus Stomoxys, plant Glossina SPP in the abdomen stable fly belongs to, lucilia sericata is planted in belonging to, and plants Auchmeromyia SPP in the Calliphora, the class fly is planted in belonging to, and plants in the Cochliomyia SPP, Carysomyia, plant in the Sarcophaga, plant in the Wohlfartia SPP, Gasterophilus, Oesteromyia SPP plants in the Oedemagena SPP., Hypoderma, the nose fly is planted in belonging to, post fly and belong to interior the kind, plant Hippobosca SPP in the Hippobosca.
Siphonaptera, for example, kind in kind, the interior kind of Echidnophaga and leaf flea belonged in objective flea belonged to.
The metaspiracle order for example, is planted in the Hyalomma, plants in the Rh, plants in the Boophilus, plants in the Amblyomma, and Haemophysalis SPP plants in the leather Tyroglyphus, plants in hard tick belongs to, and plants in the Argas, plants in the Ornithodoros, plants in residual edge tick belongs to:
The Mesastigmata order for example, is planted in the Dermanyssus, plants in the Ornithonyssus, plants in the Pneumonyssus.
Pterostigma order (prostigmata), for example, a Ji stings mite and belongs to, and psoregates SPP plants in the Myobia SPP., Demodex, plants in the Demodex:
The Astigmata order for example, is planted in the Tyroglyphus, plants in the Myocoptes SPP, Psoroptes, plant in the Trombidium, Otodects SPP plants Notoedres SPP in itch mite belongs to, Knemidocopts SPP, Neoknemidocoptes SPP, Lytodites SPP, Laminosioptes SPP.
Above-mentioned breeding poultry and feeding animals comprise Mammals such as cat, horse, sheep, pig, goat, camel, buffalo, donkey, rabbit, unpregnancy deer, reinder, fur animal (fur-bearinganimals) is as mink, chinchilla, racoon, birds such as chicken, goose, turkey, duck, fresh water and sea water fish, the fish (true trout) that belongs to fish as salmon, carp, common eel, Reptilia, insect such as honeybee and silkworm.
Laboratory animal and experimental animal comprise mouse, rat, cavy, golden hamster, dogskin cat.
Pet comprises dog and cat.
Administration can divide preventative and therapeutic is carried out.
Pass through environmental treatment, property compound itself of the present invention or give to be used through intestines or through skin with the appropriate formulation form, or by means of the special-shaped particle that comprises active compound such as ribbon, flap, bar, ring, ear, lobate band, marker is given through intestines or through skin and to be used active compound of the present invention.
Active compound can be with pulvis, rifle agent, tablet, capsule, paste, potus, granula, filling agent, pill (boli), and the form of pastille feed or tap water is through intestines, for example oral administration with.Throw and be with drops, sprays, bath agent, lotion, sprinkle and water agent and point and execute the form of agent and pulvis and finish through skin.
Appropriate formulation comprises:
Solution such as oral liquid, the dope that dilution back is oral on the skin or the solution that uses in body cavity, sprinkles and waters and point is executed preparation, coagulates agent;
For oral or through skin throw and emulsion and suspension agent, semi-solid preparation:
Wherein active compound be blended in the cream base be blended in oil-in-water or water in oil emulsion sea base matter in formulation;
Solid dosage such as pulvis, pre-mixture or dense (contracting) agent, granula, pilule, tablet, pill, capsule; Aerosol and inhalation comprise the special-shaped particle of active compound.
Solution makes by active compound is dissolved in the appropriate solvent, and, if suitable, add additive, as solubilizing agent, acid, alkali, buffering salt, oxidation inhibitor and sanitas.
The solvent that can be mentioned comprises following: physiologically acceptable solvent such as water, and pure as ethanol, butanols, phenylcarbinol, glycerine, hydro carbons, propylene glycol, polyoxyethylene glycol, N-Methyl pyrrolidone, and the mixture of these solvents.
Active compound also dissolves in the physiologically acceptable vegetables oil or synthetic oil of suitable injection if suitably.
The solubilizing agent that can be mentioned comprises following: can increase the solvency action of active compound in main solvent and maybe can prevent its sedimentary solvent.Example has polyvinylpyrrolidone, polyoxyethylenated castor oil, polyoxyethylene Isosorbide Dinitrate.
Sanitas comprises: phenylcarbinol, Trichloroisobutyl Alcohol, and right-hydroxybenzoate, propyl carbinol.
Oral liquid can directly be given and use.Dense (contracting) liquid after being diluted to administration concentration in advance again oral administration with.
The solution that uses on skin can be by dripping, brush, wiping, sprinkle or spray pattern is applied.These solution prepare as stated above.
It is favourable adding thickening material in the preparation process.Thickening material comprises: inorganic thickening agent such as wilkinite, colloidal silica, single accelerator acid aluminium, organic thickening agent such as derivatived cellulose, polyvinyl alcohol and multipolymer thereof, acrylate and methacrylic ester.
Gelifying agent is applied to, or clips on the skin, or is imported in the interior hole of body.Gelifying agent prepares by the thickening material treatment soln that can form the limpid material of cream sample denseness with capacity, and wherein said solution is to make by described method under the injectable solvent situation.Used thickening material is top further specified thickening material.
Sprinkle and to water and point is executed preparation and sprinkled and water, or splash is on the limited surface of skin, the active compound infiltration is in skin and systemic effect.
Sprinkle water and point execute preparation can be by in skin tolerance and suitable solvent or solvent mixture, dissolving, suspension or reactive emulsifying compound and prepare.If suitably, add other auxiliary such as tinting material, absorption enhancer, oxidation inhibitor, light stabilizer, and tackifier.
The solvent that can be mentioned comprises: water, alkanol, glycol, polyoxyethylene glycol, polypropylene glycol, glycerol, aromatic alcohol such as phenylcarbinol, phenylethyl alcohol, Phenoxyethanol, ester such as ethyl acetate, butylacetate, peruscabin, ether such as aklylene glycol alkyl oxide such as DPGME, the Diethylene Glycol single-butyl ether, ketone such as acetone, methylethylketone, aromatics and/or aliphatic hydrocrbon, vegetables oil or synthetic oil, DMF, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, 2,2-dimethyl-4-oxygen methylene radical-1,3-dioxolane.
Tinting material comprises that all permissions are used animal and energy is dissolved or the colorant of suspension.
The example of absorption enhancer comprises DMSO, expands oil (spreading oil) as Isopropyl myristate, dipropylene glycol pelargonate, silicone oil, fatty acid ester, triglyceride level, fatty alcohol.
Oxidation inhibitor is sulphite or burnt-sulfinate such as burnt sulfurous potassium, xitix, butylhydroxy toluene, butylated hydroxy anisole, tocopherol.
The example of light stabilizer has novantisolic acid.
The example of thickening material comprises derivatived cellulose, starch derivative, polyacrylic ester, natural polymer such as alginate, gelatin.
Emulsion agent can per os, through skin throw with or give with the injection form and to use.
Emulsion is water-in-oil-type or oil-in-water-type.
Above-mentioned these emulsions prepare as follows: the lytic activity compound is in hydrophobic or aqueous favoring and utilize the solvent of other phase, by means of suitable emulsifying agent and, if suitably, the above-mentioned phase of other auxiliary homogenizing, described auxiliary such as tinting material, absorption enhancer, sanitas, oxidation inhibitor, light stabilizer or tackifier.
The hydrophobic phase (oil) that can mention comprising: paraffin oil, silicone oil, crude vegetal such as sesame oil, Prunus amygdalus oil, Viscotrol C, synthetic glycerine three esters such as caprylic/capric Diglyceride, triglyceride level and C 8-12The mixture of long-chain vegetable fatty acid or with the mixture of other special natural acid of selecting, the partial glycerol ester mixture of saturated or unsaturated fatty acids, wherein said saturated or unsaturated fatty acids also can contain oh group, and C 8/ C 10The monoglyceride of-lipid acid and triglyceride.
Fatty acid ester such as Stearic ethyl stearate, Di-n-butyl Adipate (di-n-butyryladipate), lauric acid hexyl ester, the dipropylene glycol pelargonate, in (etc.) branched chain fatty acid and the C of chain length 16-C 18The ester that the representative examples of saturated aliphatic alcohol of chain length forms, Isopropyl myristate, Wickenol 111, C 12-C 18The caprylic/capric ester of the representative examples of saturated aliphatic alcohol of chain length, isopropyl stearate, Oleyl oleate, decyl oleate, ethyl oleate, ethyl lactate, content of wax fatty acid ester, dibutyl phthalate, the caproic acid diisopropyl ester, the ester mixture relevant with the latter, or the like.
Fatty alcohol such as different 13 (alkane) alcohol, 2-Standamul G, cetostearyl alcohol, oleyl alcohol.
Lipid acid such as oil and composition thereof.
The aqueous favoring that can mention comprises following: water, and pure as propylene glycol, glycerine, sorb (sugar) alcohol and their mixture.
The emulsifying agent that can mention comprises following: nonionogenic tenside, for example, polyoxyethylenated castor oil, the polyoxyethylene dehydrated sorbitol mono-fatty acid ester, sorbitan monostearate, glyceryl monostearate, stearic acid polyethoxye ester, alkyl phenol polyoxyethylene glycol ether;
Amphoterics such as N-lauryl-β-imino-disodium beclomethasone or Yelkin TTS;
Anion surfactant such as sodium lauryl sulphate, fatty alcohol ether sulfate, the monoethanolamine salt cats product of list/dialkyl group polyethylene glycol ether phosphate such as chlorination hexadecyl trimethyl ammonium.
Other auxiliary that can mention comprises following: the material of tackifier and stable emulsion, and as carboxymethyl cellulose, methylcellulose gum and other Mierocrystalline cellulose and starch derivative, polyacrylic ester, alginate, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, the multipolymer of methylvinylether and maleic anhydride, polyoxyethylene glycol, wax, colloidal silica, or the mixture of above-mentioned substance.
But the suspension per os or through skin throw with.They prepare by active compound is suspended in the figuration liquid, if other auxiliary of suitable adding such as wetting agent, tinting material, absorption enhancer, sanitas, oxidation inhibitor and photostabilizer.
Above-mentioned figuration liquid comprises all even solvent and solvent mixtures.
Above-mentioned wetting agent (dispersion agent) is seen upward further specified tensio-active agent.
The same institute of above-mentioned other auxiliary is indicated those auxiliarys further.
But the semi-solid preparation per os or through skin throw with.They are only owing to its high viscosity is different from above-mentioned suspension and emulsion.
For the preparation solid preparation, with active compound and suitable mixed with excipients, if suitable adding auxiliary, and as required with the mixture process preparation.
Above-mentioned vehicle comprises all physiologically acceptable solid-state inert substances.Wherein suitable comprises inorganic and organic substance.The example of inorganic substance comprises sodium-chlor, as carbonate such as lime carbonate, and supercarbonate, aluminum oxide, silicon-dioxide, carclazyte, precipitation or colloidal silica and phosphoric acid salt.
The example of organic substance comprises sugar, Mierocrystalline cellulose, food and animal-feed such as drying powdered milk, body powder (carcass meals), flour and coarse grit and starch.
Auxiliary refers to sanitas, oxidation inhibitor and tinting material, and they are further indicated already in the above.
Other suitable auxiliary comprises lubricant and antiseize paste (glidants) as Magnesium Stearate, stearic acid, and talcum, wilkinite, disintegrating agent such as starch or cross-linked polyvinylpyrrolidone, and also comprise dry adhesives such as Microcrystalline Cellulose.
Therefore, the invention still further relates to general formula (I) compound, and through type (I) compound is killed application in the verminal composition in preparation as the combatting ectoparasites agent.
It is 10ppm to 20% that ready-to-use formulation comprises concentration, the active compound of preferred 0.1% to 10% (by weight).
It is 0.5-90% that the preparation of throwing and need diluting before comprises concentration, the active compound of preferred 5-50% (hugging the weight meter).
Generally speaking, proved that now every day, every kg body weight was thrown and about 1 active compound to about 100mg amount, helped obtaining effective effect.
Except as otherwise noted, all per-cents all by weight.
The preparation of formula of the present invention (I) compound further specifies with following preparation embodiment.
Preparation embodiment
Example I b-1
Figure A9419460600581
Disperse thing to be added in the dry DMF of 5ml in the sodium hydride/mineral oil of 0.33g (0.012mol) 80% concentration, drip 2.0g (0.0062mol) 2-trifluoromethyl-4, the 20ml DMF solution of 5-two (4-fluorophenyl) imidazoles.Stirring at room mixture 30 minutes, the 5ml DMF solution of dropping 0.62g (0.0062mol) chloromethyl ethyl ether.The mixture stirring at room is inclined it in 300ml water after 3 hours and is used dichloromethane extraction (4 * 150ml) extractions.Organic phase is with dried over mgso and concentrating under reduced pressure.The residue silica gel chromatography, methylene dichloride is an eluent, provides 0.8g (33% theoretical value) 1-ethoxymethyl-2-trifluoromethyl-4,5-two (4-fluorophenyl) imidazoles is an oily body. 1H?NMR(d 6-DMSO)：δ＝1.18(t，CH 3)，3.44(q，CH 2)，5.20(s，NCH 2O)。
Example I b-2
0.65g (0.0032mol) chloromethyl 4-chlorobutyl ether is added in the 20ml dry acetone that contains 0.9g (0.0032mol) 2-trifluoromethyl-4 (5)-(4-chloro-phenyl-)-5 (4)-chlorine imidazoles and 0.48g (0.0035mol) salt of wormwood, and in stirring at room 3 hours.Filter reaction mixture and with residue acetone thorough washing, concentrating under reduced pressure filtrate.Obtain 1.4g (85% theoretical value) oily and isomery ratio and be 1-(4-neoprene oxygen ylmethyl)-2-trifluoromethyl-5-chloro-4-(4-(chloro-phenyl-) imidazoles and 1-(4-neoprene oxygen ylmethyl)-2-trifluoromethyl-4-chloro-5-(4-chloro-phenyl-) imidazole mixture of 75: 25. 1H NMR (d 6-DMSO): δ=1.7-1.9 (m, CH 2CH 2), 3.5-3.6 (m, CH 2O and CH 2Cl), 5.24 and 5.51 (are singlet, NCH in each case 2O).
Example I b-3
Figure A9419460600601
20ml THF solution with 3.00g (0.0033mol) 2-trifluoromethyl-4 (5)-(4-chloro-phenyl-)-5 (4)-chlorine imidazoles under 5 ℃ is added in the 10ml THF of 0.40g (0.013mol) 80% concentration sodium hydride/mineral oil dispersion.Continue down to stir 45 minutes at 10 ℃, and this hanging drop is added in the 20ml THF solution of 1.44g (0.011mol) acetyl-o-methyl ethanamide.After mixture refluxed 24 hours, with its cooling and incline in the 100ml frozen water, (4 * 100ml) extracted this mixture with ether.Organic phase MgSO 4Dry also concentrating under reduced pressure.Residue is chromatography on silica gel, uses cyclohexane/ethyl acetate=1: 1 to be eluent.Obtain 1.04g (35% theoretical value) N-{[2-trifluoromethyl-5-chloro-4-(4-chloro-phenyl-)-imidazoles] methyl } ethanamide, fusing point: 155-156 ℃. 1H?NMR(d 6-DMSO)：δ＝1.87(S，CH 3)，5.48(S，NCH 2N)。
Can make following formula (Ia) compound (table 1) similarly, formula (Ib) compound (table 2) and formula (Ic) compound (table 3) according to top given ordinary skill information:
Table 1
Figure A9419460600611
Embodiment number Ar Y R 1H?NMR *At CDCl 3 (a)Or d 6-DMSO (b) Isomery is than (5-Y: 4-Y replaces
Ia-1 4-Cl-C 6H 4 Br OC 2H 5 5.31(NCH 2O)， 3.68(CH 2O)， 1.26(CH 3)(b) 20∶80
Ia-2 3-Cl-C 6H 4 Br OC 2H 5 5.32(NCH 2O)， 3.68(CH 2O)， 1.29(CH 3)(b) 17∶83
Ia-3 C 6H 5 CF 3 OC 2H 5 5.37(NCH 2O)， 3.46(CH 2O)， 1.20(CH 3)(b) -
Ia-4 3，4-Cl 2- C 5H 3 Br OC 2H 5 5.32(NCH 2O)， 3.74(CH 2O)， 1.22(CH 3)(a) 14∶86
Ia-5 2-Cl-C 6H 4 Br OC 2H 5 5.25(NCH 2O)， 3.30(CH 2O)， 1.07(CH 3)(a) 19∶81
Ia-6 2-Cl-C 6H 4 Br N(CH 3)CO 2C 2H 5 5.45(NCH 2O)， 3.85(CH 2O)， 2.51(CH 3)，1.0 (CH 3)(b) 15∶85
Ia-7 2，4-Cl 2- C 6C 3 Br OC 2H 5 5.25(NCH 2O)， 3.35(CH 2O)， 0.97(CH 3)(a) 20∶80
Ia-8 4-Br-C 6H 4 Br OC 2H 5 5.37(NCH 2O)， 3.36(CH 2O)， 1.10(CH 3)(b) 20∶80
Ia-9 2，3-Cl 2- C 6H 3 Br OC 2H 5 5.23(NCH 2O)， 3.35(CH 2O)， 1.10(CH 3)，(a) 20∶80
Table 1 (continuing)
Embodiment number ?Ar ?Y ?R 1H?NMR *At CDCl 3 (a)Or d 6-DMSO (b) Isomery is than (5-Y: 4-Y replaces
Ia-10 ?2，3-Cl 2-C 6H 3 ?Br ?N(CH 3)CO 2C 2H ?5 5.30(NCH 2O)， 3.97(CH 2O)， 2.69(CH 3)， 1.64(CH 3)(a) ＜1∶99
Ia-11 ?2-Cl，6-F- ?C 6H 3 ?Br ?OC 2H 5 5.27(NCH 2O)， 3.39(CH 2O)， 1.10(CH 3)(a) 30∶70
Ia-12 ?4-CF 3-C 6H 4 ?Br ?OCH(CH 3) 2 5.33(NCH 2O)， 3.95(CH 2O)， 1.27(CH 3)， 1.25(CH 3)(a) ＜1∶99
Ia-13 ?4-CF 3-C 6H 4 ?CF 3 ?OC 2H 5 5.36(NCH 2O)， 3.55(CH 2O)， 1.28(CH 3)(a) -
Ia-14 ?4-Cl-C 6H 4 ?CF 3 ?OC 2H 5 5.34(NCH 2O)， 3.54(CH 2O)， 1.24(CH 3)(a) -
Ia-15 ?3，4-Cl 2-C 6H 3 ?CF 3 ?OC 2H 5 5.35(NCH 2O)， 3.54(CH 2O)， 1.27(CH 3)(a) -
Ia-16 ?3-Cl-C 6H 4 ?CF 3 ?OC 2H 5 5.34(NCH 2O)， 3.55(CH 2O)， 1.25(CH 3)(a) -
Ia-17 ?3，4-O-CFCl- ?CFCl-O-C 6H 3 ?CF 3 ?OC 2H 5
Ia-18 ?4-CF 3-C 6H 4 ?Br ?OC 2H 5 5.25(NCH 2O)， 3.38(CH 2O)， 1.12(CH 3) 20∶80
*Given data are the NMR data of main isomer under all scenario (8 values are unit with ppm; TMS is interior mark).
Table 2
Embodiment number ?Ar Y ?R 1H?NMR *At CDCl 3 (a)Or d 6-DMSO (b) Isomery is than (5-Y: 4-Y replaces
Ib-4 ?4-Br-C 6H 4 Cl ?OC 2H 5 5.50(NCH 2O)， 3.62(CH 2O)，1.23 (CH 3)(a) 93∶7
Ib-5 ?4-Br-C 6H 4 Cl ?N(CH 3)CO 2CH 3 5.60(NCH 2N)， 3.80(NCH 3)，2.90 (CO 2CH)(a) 78∶22
Ib-6 ?4-Cl-C 6H 4 Cl ?OC 2H 5 5.50(NCH 2O)， 3.65(OCH 2)，1.21 (CH 3)(a) 86∶14
Ib-7 ?4-Cl-C 6H 4 Cl ?OCH 2CH 2CH 2CH 2Cl 5.51(NCH 2O)， 3.55(CH 2O)，3.55 (CH 2Cl)(a) 75∶25
Ib-8 ?4-NO 2- ?C 6H 4 Cl ?OC 2H 5 5.54(NCH 2O)， 3.62(CH 2O)，1.25 (CH 3)(a) 99∶1
Ib-9 ?3-Cl-C 6H 4 Cl ?OC 2H 5 5.51(NCH 2O)， 3.60(CH 2O)，1.23 (CH 3)(a) 87∶13
Ib-10 ?3，4-Cl 2- ?C 6H 3 Cl ?OC 2H 5 5.51(NCH 2O)， 3.62(CH 2O)，1.24 (CH 3)(a) 93∶7
Ib-11 ?4-Cl-C 6H 4 Cl ?On-C 4H 9 5.50(NCH 2O)， 3.53(CH 2O)，0.89 (CH 3)(a) ＞99∶1
Ib-12 ?4-Cl-C 6H 4 Cl ?O-iPr 5.53(NCH 2O)， 3.53(OCH)，1.13 (CH 3)(b) ＞99∶1
Ib-13 ?4-Cl-C 6H 4 Cl ?4-Cl-(C 6H 4) 5.32(NCH 2)(a) ＞99∶1
Ib-14 ?4-Cl-C 6H 4 Cl ?NHCOCH 3 5.48(NCH 2N)， 1.87(b) ＞99∶1
Ib-15 ?4-F-C 6H 4 4-F-(C 6H 4) ?OC 2H 5 5.20(NCH 2O)， 3.44(CH 2O)，1.18 (CH 3)(b) -
Ib-16 ?3-NO 2， ?5-CF 3- ?C 6H 3 3-NO 2， 5-CF 3-(C 6H 3) ?OC 2H 5 5.25(NCH 2O)， 3.50(CH 2O)，1.21 (CH 2)(b) -
Table 2-is continuous
Embodiment number Ar Y ?R 1H?NMR *At CDCl 3 (a)Or d 6-DMSO (b) Isomery is than (5-Y: 4-Y replaces
Ib-17 4-Cl-C 6H 4 Br ?OC 2H 5 5.55(NCH 2O)， 3.58(CH 2O)，1.13 (CH 3)(b) 80∶20
Ib-18 4-Cl-C 6H 4 Br ?CH(CH 3) 2 5.54(NCH 2O)， 3.81(CH)，1.14 (CH 3)(b) 81∶19
Ib-19 4-Cl-C 6H 4 Br ?NHCOCH 3 5.50(NCH 2O)， 1.88(CH 3)(b) 79∶21
Ib-20 4-F-C 6H 4 Br ?OC 2H 5 5.56(NCH 2O)， 3.61(CH 2O)，1.12 (CH 3)，(b) 83∶17
Ib-21 3-NO 2- C 6H 4 Br ?OC 2H 5 5.57(NCH 2O)， 3.60(CH 2O)，1.13 (CH 3)(b) 80∶20
Ib-22 2，4-Cl 2- C 6H 3 Cl ?OC 2H 5 5.58(NCH 2O)， 3.58(CH 2O)，1.16 (CH 3)(b) 55∶44
Ib-23 2，4-Cl 2- C 6H 3 Br ?OC 2H 5 5.56(NCH 2O)， 3.50(CH 2O)，1.15 (CH 3)(b) 85∶15
Ib-24 2-Cl， 6-F-C 6H 3 Br ?OC 2H 5 5.56(NCH 2O)， 3.61(CH 2O)，1.25 (CH 2)(a) 60∶40
Ib-25 4-CF 3- C 6H 4 Cl ?OC 2H 5 5.53(NCH 2O) 23.61(CH 2O)，1.24 (CH 3)(a) 82∶18
Ib-26 4-CF 3- C 6H 4 Br ?OC 2H 5 5.58(NCH 2O)， 3.63(CH 2O)，1.14 (CH 3)(b) 85∶15
Ib-27 4-OCF 3- C 6H 4 Cl ?OC 2H 5 5.54(NCH 2O)， 3.62(CH 2O)，1.24 (CH 3)(a) 79∶21
Ib-28 4-OCF 3- C 6H 4 Br ?OC 2H 5 5.53(NCH 2O)， 3.60(CH 2O)，1.24 (CH 3)(a) 80∶20
Ib-29 3-Br， 4-F-C 6H 3 Cl ?OC 2H 5
Ib-30 3，5-Cl 2- C 6H 3 Cl ?OC 2H 5 5.56(NCH 2O)， 3.57(CH 2O)，1.13 (CH 3)(b)
Ib-31 2，3-Cl 2- C 6H 3 Cl ?OC 2H 5 5.58(NCH 2O)， 3.59(CH 2O)，1.14 (CH 3)(b) 70∶30
Ib-32 2，3-Cl 2- C 6H 3 Br ?OC 2H 5 5.57(NCH 2O)， 3.58(CH 2O)，1.12 (CH 2)(b) 60∶40
Table 2-is continuous
Embodiment number ?Ar Y R 1H?NMR *At CDCl 3 (a)Or d 6-DMSO (b) Isomery is than (5-Y: 4-Y replaces
Ib-33 ?4-Cl-C 6H 4 4-Cl(C 6H 4) OC 2H 5
Ib-34 ?3，4-Cl 2-C 6H 3 3，4- Cl 2(C 6H 3) OC 2H 5 5.31(NCH 2O)， 5.30(CH 2O)， 1.10(CH 2)(b) ?70∶30
Ib-35 ?2-Cl-C 6H 4 2-Cl(C 6H 3) OC 2H 5 5.29(NCH 2O)， 3.30(CH 2O)， 1.01(CH 2)(a) ?-
Ib-36 ?4-Br-C 6H 4 4-Br(C 6H 4) OC 2H 5 5.19(NCH 2O)， 3.43(CH 2O)， 1.17(CH 2)(a)
Ib-37 ?3，4- ?OCFClCFCl-O- ?C 6H 3 Br OC 2H 5 5.31(NCH 2O)， 3.30(CH 2O)， 1.10(CH 2)(b) ?60∶40
Ib-38 ?3，4-Cl 2-C 6H 3 Cl OCH(CH 3) 2 5.54(NCH 2O)， 3.82(CHO)， 1.14(CH 2)， 1.12(CH 2)(b) ?85∶15
Ib-39 ?3，4-Cl 2-C 6H 3 C1 OCH 2OCH 2CH 2OCH 3 5.59(NCH 2O)， 3.69(CH 2O)， 3.54(CH 2O)， 3.46(OCH 3) (b) ?85∶15
Ib-40 ?3，4-Cl 2-C 6H 3 Cl O(CH 2) 3CH 3 5.50(NCH 2O)， 3.53(CH 2O)， 1.60(CH 2)， 0.89(CH)(b) ?＞99∶1
Ib-41 ?3，4-Cl 2-C 6H 3 Cl OCH 2(4-Cl-C 6H 4) 6.11(NCH 2O)， (b) ?＞99∶1
Ib-42 ?3，4-Cl 2-C 6H 3 Cl OCH 2C≡C-CH 2Cl 5.60(NCH 2O)， 4.32(CH 2O)， 4.12(CH 2Cl) (b) ?＞99∶1
Ib-43 ?3，4-Cl 2-C 6H 3 Cl O-CH(CH 2F) 2 5.70(NCH 2O)， 4.51(CH 2F)， 4.19(CHO)(b) ?＞99∶1
Ib-44 ?3，4-Cl 2-C 6H 3 NO 2 OC 2H 5
Ib-45 ?3，4-Cl 2-C 6H 3 SCF 3 OC 2H 5
Ib-46 ?3，4-Cl 2-C 6H 3 SOCF 3 OC 2H 5 5.55(NCH 2O)， 3.58(CH 2O)， 1.15(CH 2)(b) ?＞99∶1
Ib-47 ?3，4-(OCF 2CHFCl ?) 2-C 6H 3 Br OC 2H 5 6.40(CHF)， 5.24(NCH 2O)， 3.64(CH 2O)， 1.24(CH 2)(a) ?＞99∶1
Ib-48 ?4-Cl-C 6H 4 Br N(CH 3)CO 2CH 3 2.77(N-CH 2)， 3.69(OCH 2)， 5.74(CH 2)(b) ?＞99∶1
Ib-49 ?3-Br，4-F-C 6H 3 Br OC 2H 5 5.57(NCH 2O)， 3.58(CH 2O)， 1.12(CH 3)(b) ?80∶20
Ib-50 ?3-Br，4-F-C 6H 3 Br N(CH 3)CO 2C 2H 5 5.77(NCH 2N)， 4.24(OCH 2)， 2.81(N-CH 2) 1.28(CH 3) ?＞99∶1
*Given data are the NMR data of main isomer under all scenario (8 values are unit with ppm; TMS is interior mark).
Table 3
Figure A9419460600661
Embodiment number ??Ar Y R 1H?NMR *At CDCl 3 (a)Or d 6-DMSO (b) Isomery is than (5-CF 2∶ 4-CF 3Replace on)
Ic-1 4-Cl-C 6H 4 CF 3 OC 2H 5 5.26(NCH 2O)， 3.35(OCH 2)，0.97 (CH 3)(b) 21∶79
Ic-2 4-Cl-C 6H 4 Br OC 2H 5 5.13(NCH 2O)， 3.34(OCH 3)，1.01 (CH 3)(b) 30∶70
Ic-3 4-Cl-C 6H 4 4-Cl(C 6H 4) OC 2H 5 5.03(NCH 3O)， 3.26(OCH 2)，0.97 (CH 3)(b) 96∶4
Ic-4 4-Cl-C 6H 4 Cl OC 2H 5 5.11(NCH 2O)， 3.51(OCH 2)，1.19 (CH 3)(a) 42∶58
Ic-5 4-Cl-C 6H 4 CN OC 2H 5
Ic-6 2，4-Cl 2- C 6H 3 CF 3 OC 2H 5 5.25(NCH 2O)， 3.34(OCH 2)，1.01 (CH 3) 70∶30
Ic-7 2，4-Cl 2- C 6H 3 Br OC 2H 5
Ic-8 3，4-Cl 2- C 6H 3 CF 3 OC 2H 5 5.26(NCH 2O)， 3.35(OCH 2)，0.97 (CH 3)(b) 70∶30
Ic-9 3，4-Cl 2- C 6H 3 Br OC 2H 5
Ic-10 3-Cl-C 6H 4 CF 3 OC 2H 5
Ic-11 3-Cl-C 6H 4 Br OC 2H 5
Ic-12 4-Br-C 6H 4 Br OC 2H 5
Ic-13 2，4-Cl 2- C 6H 3 Cl OC 2H 5
Ic-14 2，3-Cl 2- C 6H 3 CF 3 OC 2H 5
Ic-15 2，3-Cl 2- C 6H 3 Br OC 2H 5
Ic-16 4-CF 3- C 6H 4 CF 3 OC 2H 5 5.26(NCH 2O)， 3.35(OCH 2)，0.97 (CH 3)(b) 70∶30
Ic-17 4-CF 3- C 6H 4 Br OC 2H 5
Ic-18 3，4-Cl 2- C 6H 2 Cl OC 2H 5
Ic-19 2，3-Cl 2- C 6H 3 Cl OC 2H 5
Ic-20 4-CF 3- C 6H 4 Cl OC 2H 5
Table 3-is continuous
Embodiment number Ar Y R 1H?NMR *At CDCl 3 (a)Or d 6-DMSO (b) Isomery is than (5-CF 3∶ 4-CF 3Replace
Ic- 21 3，4-Cl 2- C 6H 3 CF 3 N(CH 3)CO 2C 2H 5 5.30(NCH 2O)， 3.97(CH 2O)， 2.69(CH 3)，1.64 (CH 3)(a) ＞99∶1
Ic- 22 3，4-Cl 2- C 6H 3 CN ?OC 2H 5 5.12(NCH 2O)， 3.52(CH 2O)， 1.22(CH 3) ＞99∶1
*Given data are the NMR data of main isomer under all scenario (8 values are unit with ppm; TMS is interior mark).
Example I c-23
Figure A9419460600681
5.0g (0.0128mol) 1-ethoxyl methyl-2-formyl radical-4-(3, the 4-dichlorophenyl)-5-trifluoromethyl imidazoles and 1.0g (0.014mol) oxammonium hydrochloride (hydroxylammonium Chloride) were stirred 2 hours under room temperature in the 50ml pyridine.Be added dropwise to the 10ml acetic anhydride and mixture is descended stirring 4 hours in 60-70 ℃.After the cooling, with in the reaction mixture impouring 300ml water and use CH 2Cl 2Extract, dry organic phase and vacuum are removed solvent.Crude product is by silica gel column chromatography, uses cyclohexane/ethyl acetate=be eluent at 2: 1, provides the compound of 1.60g (34% theoretical value) shown in top, is oil form. 1H?NMR(CDCl 3)：δ＝7.2-7.8(m，3H)；5.12(S，2H)；3.52(q，2H)；1.22(t，3H)。
Example I c-24
According to top given relevant preparation-as information, can make the following formula compound similarly, its ratio is 70: 30. 1H?NMR(CDCl 3)：δ＝5.06(CH 2)，3.50(CH 2)；1.17(CH 3)。The preparation of initial compounds.
Example II a-1
Figure A9419460600692
Sodium hydride/the mineral oil of 0.90g (0.030mol) 80% concentration is added in the dry DMF of 20ml, and in 0 ℃ to the 20ml DMF solution that wherein is added dropwise to 5.0g (0.0158mol) N-(2-chloro-1,1,1,4,4,4-chlordene-3-chloro-2-butylene-2-yl) benzamidine.After adding, stirring at room mixture 1 hour and in 80 ℃ of restir 5 hours.Reaction mixture, and with (3 * 150ml) extract in its impouring 300ml frozen water and with ethyl acetate.Dry organic phase, solvent is removed in decompression, and the residue thing is passed through silica gel column chromatography, uses methylene dichloride to provide 1.10g (25% theoretical value) 2-phenyl-4,5-two (trifluoromethyl) imidazoles, fusing point: 120-123 ℃ as eluent.
Example II b-1
Be dissolved in 3.0g (0.011mol) 2-trifluoromethyl-4 (5)-(4-nitrophenyl)-imidazoles and 0.9g (0.011mol) sodium acetate in the 20ml Glacial acetic acid and add the chlorine glacial acetic acid solution (0.012mol) of 13.5g6.3% concentration.After 30 minutes, all raw materials are all reacted, and will leach precipitated reaction products in the reaction mixture impouring 100ml water, and washing is also dry.Obtain 1.84g (52% theoretical value) 2-trifluoromethyl-4 (5)-(4-nitrophenyl)-5 (4)-chloro imidazoles, fusing point: 180-183 ℃.
Example II b-2
40ml Glacial acetic acid and 2.64g (0.107mol) bromine are added drop-wise within 5.0g (0.015mol) 2-trifluoromethyl-4 (5)-(4-trifluoromethyl) imidazoles and 1.2g (0.015mol) sodium acetate.1.5 after hour, add the 0.5g bromine again, and continue to stir 1 hour in room temperature.In the reaction mixture impouring 300ml water, leach reaction product and at air drying.Obtain 5.0g 2-trifluoromethyl-4 (5)-(4-trifluoromethyl)-5 (4)-bromo imidazoles (93% theoretical value), fusing point: 210 ℃.
Example II b-3
Figure A9419460600711
Under the room temperature, in batches with 5.0g (0.018mol) 4 (5)-(3, the 4-dichlorophenyl)-and the 2-trifluoromethyl imidazoles very is added in the mixture of 10ml oleum and 10ml 96% concentration nitric acid carefully, and continue stirring at room 2 hours, and reaction mixture is poured in the 300ml frozen water.Suction filtration goes out the product that is settled out and at air drying.Obtain 5.7g (97% theoretical value) 4 (5)-(3, the 4-dichlorophenyl)-2-trifluoromethyl imidazoles, fusing point: 227-229 ℃.
Example II c-1
Figure A9419460600712
3.4g (0.0138mol) 4 (5)-(4-chloro-phenyl-)-5 (4)-trifluoromethyl imidazoles are dissolved in the 60ml Glacial acetic acid, add the 1.5g ammonium acetate, be heated to the 10ml glacial acetic acid solution that ebullient is added dropwise to 2.64g (0.0165mol) bromine simultaneously at above-mentioned solution.After 1 hour, reaction mixture and with in its impouring 400ml water leaches sedimentary product, and washing is also dry.Get 3.2g (71% theoretical value) 2-bromo-4 (5)-(4-chloro-phenyl-)-5 (4)-trifluoromethyl imidazoles, fusing point 195-197 ℃.
Example II c-2
2.9g (0.0089mol) 2-bromo-4 (5)-(4-chloro-phenyl-)-5 (4)-trifluoromethyl imidazoles are dissolved among the 30ml DMF and in 120 ℃ to wherein by dry HCl gas 3 hours.Mixture kept under this temperature 2 hours subsequently again.In the reaction mixture impouring 300ml frozen water, leach the precipitation and the drying that are produced.Get 2.3g (92% theoretical value) 2-chloro-4 (5)-(4-chloro-phenyl-)-5 (4)-trifluoromethyl imidazoles, fusing point 205-207 ℃.
Example II c-3
Figure A9419460600722
With 8.00g (0.0314mol) 1-(4-chloro-phenyl-)-3,3,3-three fluoro-1,2-propanedione-hydrate and 20g amine acetate are added in the 100ml Glacial acetic acid, and are added dropwise to 5.66g (0.0393mol) the trifluoro acetaldehyde alcoholic acid 20ml ice aldehydic acid solution that contracts.Mixture heating up boiling added 5.66g (0.0393mol) the trifluoro acetaldehyde ethanolic soln that contracts in 1.5 hours again.Under boiling point, reacted 3 hours again, reaction mixture, and in the impouring 400ml frozen water, neutralize with 25% concentration ammonia solution.Leach the reaction product that is settled out, washing is also dry.Use the normal hexane recrystallization, obtain 2.5g (25% theoretical value) 2-trifluoromethyl-4 (5)-(4-chloro-phenyl-)-5 (4)-trifluoromethyl imidazoles, fusing point 192-195 ℃.
Example II c-4
Figure A9419460600731
With 8.0g (0,0393mol) 1-(4-chloro-phenyl-)-3,3,3-three fluoro-1,2-propanedione-hydrate and 20g ammonium acetate are dissolved in the 100ml Glacial acetic acid, add 5.7g (0.037mol) 4-chlorobenzaldehyde, and solution was heated 18 hours under boiling point.After the cooling, in the reaction mixture impouring 600ml frozen water and with the neutralization of 25% concentration ammonia solution, leach the product that is settled out, washing is also dry.Silica gel column chromatography, methylene dichloride are eluent, get 6.7g (61% theoretical value) 2,4 (5)-two-(4-chloro-phenyl-)-5-(4)-trifluoromethyl imidazoles, fusing point: 233-236 ℃.
According to top given technical intelligence, the preparation embodiment that is similar to the above-mentioned raw materials compound can prepare following new imidazoles:
Table 4
Embodiment number ????Ar ????Y Fusing point [℃]
??IIa-2 ????C 6H 4 ????CF 3 ????120-123
??IIa-3 ????4-CF 3-C 6H 4 ????CF 3 ????176-177
??IIa-4 ????4-Cl-C 6H 4 ????CF 3 ????167-169
??IIa-5 ????3，4-Cl-C 6H 3 ????CF 3 ????170-171
??IIa-6 ????3-Cl-C 6H 4 ????CF 3 ????155-157
??IIa-7 ????3，4-O-CFCl- ????CFCl-O-C 6H 3 ????CF 3
Table 5
Figure A9419460600751
Embodiment number ????Ar ????Y Fusing point [℃]
IIb-4 ????4-Cl-C 6H 4 ????Cl ????154-156
IIb-5 ????4-Cl-C 6H 4 ????Br ????186-187
IIb-6 ????3-Cl-C 6H 4 ????Cl ????167-169
IIb-7 ????3，4-Cl 2-C 6H 3 ????Cl ????181-183
IIb-8 ????3，4-Cl 2-C 6H 3 ????Br ????200-201
IIb-9 ????3，4-Cl 2-C 6H 3 ????NO 2 ????227-229
IIb-10 ????3，4-Cl 2-C 6H 3 ????SCF 3 ????195-196
IIb-11 ????3，4-Cl 2-C 6H 3 ????SOCF 3 ????203-204
IIb-12 ????2，4-Cl 2-C 6H 3 ????Cl
IIb-13 ????2，3-Cl 2-C 6H 3 ????Br
IIb-14 ????2，3-Cl 2-C 6H 3 ????Cl ????200-203
IIb-15 ????3，5-Cl 2-C 6H 3 ????Cl ????222
IIb-16 ????4-F-C 6H 4 ????Br ????158-159
IIb-17 ????3-NO 2-C 6H 4 ????Br ????175-177
IIb-18 ????2-Cl，6-F-C 6H 3 ????Br ????216-218
IIb-19 ????4-CF 3-C 6H 4 ????Cl ????185-187
IIb-20 ????4-CF 3-C 6H 4 ????Br ????210-211
IIb-21 ????4-OCF 3-C 6H 4 ????Cl ????153-155
IIb-22 ????4-OCF 3-C 6H 4 ????Br ????184-186
IIb-23 ????3-Br，4-F-C 6H 3 ????Cl ????187-189
IIb-24 ????3，4- ????OCFClCFCl-O- ????C 6H 3 ????Br ????oil
IIb-25 ????3，4- ????(OCF 2CHFCl) 2- ????C 6H 3 ????Cl
IIb-26 ????4-Br-C 6H 4 ????Cl ????185-187
IIb-27 ????4-NO 2-C 6H 4 ????Cl ????180-183
Table 5-is continuous
Embodiment number ????Ar ????Y Fusing point [℃]
IIb-28 ????2，4-Cl 2-C 6H 3 ????Br ????222-223
IIb-29 ????3-Br，4-F- ????C 6H 3 ????Br ????173-174
IIb-30 ????3，4- ????(OCF 2CHFCl) 2- ????C 6H 3 ????Br ????oil
Example II b-31
Figure A9419460600761
6.8g (0.024mol) 4-(3, the 4-dichlorophenyl)-2-trifluoromethyl imidazoles is dissolved in the 150ml methylene dichloride, in solution, adds excessive trifluoromethylthio chlorine solution.Continue to stir and spend the night, and vacuum is removed solution.Gained residue silica gel column chromatography, cyclohexane/ethyl acetate=4: 1 are eluent, obtain 3.15g (34% theoretical value) above-claimed cpd, fusing point: 195-196 ℃.
Example II b-32
10ml CH with the 2.3g metachloroperbenzoic acid 2Cl 2Solution is added in the 200ml dichloromethane solution of 2.1g (0.0055mol) 4 (5)-(3, the 4-dichlorophenyl)-2-trifluoromethyl-5 (4)-trifluoromethyl sulfonyl imidazoles (made by example II b-31), and with above-mentioned solution stirred overnight at room temperature.Use saturated NaHCO in succession 3Solution (1 * 50ml), saturated NaHCO 3Solution (2 * 50ml) and water (2 * 50ml) wash and use MgSO 4Drying, vacuum is removed solvent.Silica gel column chromatography (eluent CH 2Cl 2) afterwards, get 0.55g (25% theoretical value) above-claimed cpd, fusing point 205-206.
Table 6
Embodiment number ????Ar ????Y Fusing point [℃]
??IIc-5 ??4-Cl-C 6H 4 ??CF 3 ??192-194
??IIc-6 ??4-Cl-C 6H 4 ??Br ??195-197
??IIc-7 ??4-Cl-C 6H 4 ??Cl ??205-207
??IIc-8 ??4-Cl-C 6H 4 ??4-Cl-C 6H 4 ??233-235
??IIc-9 ??4-Cl-C 6H 4 ??CN
??IIc-10 ??2，4-Cl 2-C 6H 3 ??CF 3 ??208-209
??IIc-11 ??2，4-Cl 2-C 6H 3 ??Br
??IIc-12 ??2，4-Cl 2-C 6H 3 ??Cl
??IIc-13 ??3，4-Cl 2-C 6H 3 ??CF 3 ??179-180
??IIc-14 ??3，4-Cl 2-C 6H 3 ??Br
??IIc-15 ??3，4-Cl 2-C 6H 3 ??Cl
??IIc-16 ??3-Cl-C 6H 4 ??CF 3
??IIc-17 ??3-Cl-C 6H 4 ??Br
??IIc-18 ??3-Cl-C 6H 4 ??Cl
??IIc-19 ??2，3-Cl 2-C 6H 3 ??CF 3
??IIc-20 ??2，3-Cl 2-C 6H 3 ??Br
??IIc-21 ??2，3-Cl 2-C 6H 3 ??Cl
??IIc-22 ??4-CF 3-C 6H 4 ??CF 3 ??203-205
??IIc-23 ??4-CF 3-C 6H 4 ??Br
??IIc-24 ??4-CF 3-C 6H 4 ??Cl
Example II c-25
Figure A9419460600791
2.0g (0.005mmol) 1-ethoxymethyl-2-cyano group-4 (5)-(3, the 4-dichlorophenyl)-5 (4)-trifluoromethyl imidazoles were heated 2 hours down in 80-90 ℃ in 200ml 20% concentration hydrochloric acid, and after the cooling, mixture is with dichloromethane extraction and use MgSO 4Drying, vacuum is removed solvent.Get on the 1.2g (78% theoretical value) and show compound, fusing point: 186-188 ℃.
Example II c-26
Figure A9419460600792
According to aforesaid general technology information can make similarly above shown in compound, mp:202-204 ℃.
Example VII A-1
Be dissolved in 30.0g (0.20mol) benzamidine in the 300ml acetonitrile and add 80g (0.80mol) triethylamine.Be added dropwise to 46.0g (0.20mol) 2 at 65 ℃, 3-dichloro hexafluoro-2-butylene, and with mixture stirring and refluxing 15 hours.Solvent is removed in decompression, and residue pours in the 200ml water and with methyl tertiary butyl ether and extracts, and organic phase is with 5% concentration hydrogen sodium hydroxide solution and water washing, dry also solvent removed in vacuo.After the molecular distillation, get 26g (41% theoretical value) N-(3-chloro-1,1,1,4,4,4-hexafluoro-2-butylene-2-yl)-benzamidine, boiling point (0.05 mmhg): 104 ℃.
Example VII A I-1
3.69g (0.045mol) sodium acetate and the 40ml methanol solution that contains 9.74g (0.045mol) 2 '-amino-4-nitro-phenyl methyl ketone hydrochloride are added to the methanol solution of the trifluoromethyl acetimidic acid methyl esters of 19.8g (0.05mol) 32% concentration, and, under boiling temperature, stirred 1.5 hours then mixture stirring at room 2 hours.After the cooling, in the reaction mixture impouring 100ml water, leach the precipitation that is settled out, the water thorough washing is also dry.Crude product is with silica gel purification (cyclohexane/ethyl acetate=be eluent at 1: 1), must 3.69g (31% theoretical value) 2-trifluoromethyl-4 (5)-4-nitrophenyl imidazoles, and fusing point: 208 ℃.
Example I X-1
Figure A9419460600811
With 10.0g (0.0393mol) 1-(4-chloro-phenyl-)-3,3,3-three fluoro-1,2-propanedione-hydrate, 1.09g (0.0078mol) urotropine and 20g ammonium acetate heated 2 hours under boiling temperature in the 100ml Glacial acetic acid.After the cooling, solution inclines in the 300ml frozen water, and mixture neutralizes with 25% concentration ammonia solution.Leach the product that is settled out, washing is also dry.Use the toluene recrystallization, get 3.8g (39% theoretical value) 4 (5)-(4-chloro-phenyl-)-5 (4)-trifluoromethyl imidazoles, fusing point: 240-243 ℃.
Embodiment XV-1
Figure A9419460600812
20.0g (0.06mol) 4-(3, the 4-dichlorophenyl)-5-trifluoromethyl imidazoles is same as under the room temperature to stir with 11.3g (0.12mol) chloromethyl ethyl ether and 16.6g (0.12mol) salt of wormwood one in the 100ml acetonitrile spends the night.Vacuum concentration reaction mixture, residue are dissolved in 100ml methylene dichloride and the 100ml water, organic phase MgSO 4Drying, and remove and desolvate, get 11.23g (57% theoretical value) 1-ethoxymethyl-4 (5)-(3, the 4-dichlorophenyl)-5 (4)-trifluoromethyl imidazoles, be an oily body, this product is used for next step reaction with the crude product form.
In argon atmospher, protected imidazoles of the above-mentioned N-of 5.7g (0.016mol) and 50ml THF solution are cooled to-70 ℃, are added dropwise to the hexane solution of 12ml (0.018mol) 1.6M n-Butyl Lithium.Continue to stir 15 minutes, under-70 ℃, be added dropwise to the 5ml THF solution of 1.8g (0.024mol) DMF then.Make mixture return to ambient temperature overnight, add 20ml water, and with saturated ammonium chloride solution with pH regulator to 7.(3 * 100ml) extract MgSO to product with ethyl acetate 4Drying, and solvent removed in vacuo obtain showing compound on the 5.6g (95% theoretical value), are an oily body. 1H?NMR(CDCl 3)δ＝9.45(s，1H)；7.2-7.8(m，3H)；5.11(s，2H)；3.52(q，2H)；1.21(t，3H).
The biological effect of formula of the present invention (I) compound is illustrated with reference to following embodiment.In most of the cases, only illustrate according to preparation embodiment a kind of isomer of the isomer mixture that may exist, and under this Ministry of Finance, they are tested.
Embodiment A
The chrysomelid larva test solvent of ape: 7 weight part dimethyl formamide emulsifying agents: 1 weight part alkaryl polyglycol ether
Be the appropriate formulation of preparation active compound, with 1 part of weight active compound and above-mentioned amount solvent and above-mentioned amount emulsifier mix, and water is diluted to desirable concentration with enriched material.
Handle in the preparation of the active compound by the leaf of Brassica oleracea L.var.capitata being immersed desired concn and under leaf still keeps moist situation, infect with the chrysomelid larva of horseradish ape.
After the specified time cycle, measure the degree of representing with % of killing.100% means all, and the horseradish ape is chrysomelid all is killed, and 0% means chrysomelid being killed of no horseradish ape.
In this test, the compound that for example prepares example I a-4, Ia-7, Ib-4, Ib-5, Ib-6, Ib-15, Ib-17, Ib-18 and Ic-1 demonstrated 100% killing rate after 3 days under 0.1% activity compound concentration of demonstration.
Table A
To the chrysomelid larva test of the deleterious insect ape of plant
Figure A9419460600841
Table A-continuous
To the chrysomelid larva test of the deleterious insect ape of plant
Figure A9419460600851
Table A-continuous
To the chrysomelid larva test of the deleterious insect ape of plant
Figure A9419460600861
Embodiment B
Diamond-back moth test solvent: 7 weight part dimethyl formamide emulsifying agents: 1 weight part alkaryl polyglycol ether
For the appropriate formulation of preparation active compound,, and this enriched material is diluted with water to the concentration of wanting with 1 part of weight active compound and above-mentioned amount solvent and above-mentioned amount emulsifier mix.
The wild cabbage leaf is wanted by being immersed in handle in the preparation of active compound of concentration, and under the still moist situation of leaf, infected with the diamond-back moth larva.
After the specified time cycle, measure the degree of representing with % of killing.100% means all above-mentioned larvas is killed, and 0% means no larva is killed.
In this test, the compound that for example prepares example I a-4, Ia-7, Ib-4, Ib-5, Ib-6, Ib-15, Ib-17, Ib-18 and Ic-1 demonstrated 100% killing rate after 3 days under 0.1% activity compound concentration of demonstration.
Table B
To the deleterious insect diamond-back moth test of plant
Figure A9419460600871
Table B-is continuous
To the deleterious insect diamond-back moth test of plant
Table B-is continuous
To the deleterious insect diamond-back moth test of plant
Figure A9419460600891
Embodiment C
Heliothis virescens test solvent: 7 weight part dimethyl formamide emulsifying agents: 1 weight part alkaryl polyglycol ether
For the appropriate formulation of preparation active compound,, and this dope is diluted with water to the concentration of wanting with 1 part of weight active compound and above-mentioned amount solvent and above-mentioned amount emulsifier mix.
Big bean sprouts is immersed in the active agent preparations of the concentration of wanting and handles, and under the still moist situation of leaf, infect with the Heliothis virescens larva.
After the specified time cycle, measure the degree of representing with % of killing.100% means all larvas all is killed, and 0% means no larva is killed.
In this test, the compound that for example prepares example I a-4, Ia-7, Ib-4, Ib-5, Ib-6, Ib-15, Ib-17, Ib-18 and Ic-1 demonstrated 100% killing rate after 3 days under 0.1% activity compound concentration of demonstration.
Table C
To the deleterious insect Heliothis virescens test of plant
Figure A9419460600901
Table C-is continuous
To the deleterious insect Heliothis virescens test of plant
Table C-is continuous
To the deleterious insect Heliothis virescens test of plant
Embodiment D
Leafhopper test solvent: 7 weight part dimethyl formamide emulsifying agents: 1 weight part alkaryl polyglycol ether
For the appropriate formulation of preparation active compound,, and this dope is diluted with water to the concentration of wanting with 1 part of weight active compound and above-mentioned amount solvent and above-mentioned amount emulsifier mix.
The active agent preparations that rice seedling is immersed in the concentration of wanting is handled, and infects with the rice green leafhopper larva under the still moist situation of rice seedling.
After the specified time cycle, measure the degree of representing with % of killing.100% means all above-mentioned jassidss all is killed; 0% means no jassids is killed.
In this test, the compound that for example prepares example I a-4, Ia-7, Ib-4, Ib-5, Ib-6, Ib-17, Ib-18 and Ic-1 demonstrated at least 90% killing rate after 6 days under 0.1% activity compound concentration of demonstration.
Table D
To the deleterious insect leafhopper test of plant
Figure A9419460600931
Table D-is continuous
To the deleterious insect leafhopper test of plant
Figure A9419460600941
Embodiment E
Tetranychid test (OP resistivity) solvent: 7 weight part dimethyl formamide emulsifying agents: 1 weight part alkylaryl polyglycol ether
Be the appropriate formulation of preparation active compound, with 1 part of weight active compound and above-mentioned amount solvent and above-mentioned amount emulsifier mix, and water is diluted to the concentration of wanting with dope.
To be immersed in the active agent preparations of the concentration of wanting by the beans tannin plant that the greenhouse tetranychus telarius of all etap seriously infects.
After the specified time cycle, measure the degree of representing with % of killing.100% means all tetranychids all is killed; 0% represents that then no tetranychid is killed.
In this test, the compound that for example prepares example I b-4, Ib-5 and Ib-6 demonstrated at least 98% killing rate after 7 days under 0.1% activity compound concentration of demonstration.
Table E
To the deleterious insect tetranychid test of plant (OP resistivity)
Figure A9419460600961
Embodiment F
Mythimna separata test solvent: 31 weight part acetone emulsifying agents: 1 weight part alkylaryl gathers ethanol ether
For the appropriate formulation of preparation active compound, with 1 part of weight active compound and above-mentioned amount solvent and above-mentioned amount emulsifier mix, and this dope of dilute with water is to the concentration of wanting.
Draw specified amount and want the preparation of concentration active compound, place on the standard synthetic diet.In each case with a meadow armyworm larvae (L 3) place on the feed.Test repeats six times.
After the specified time cycle, measure the degree of representing with % of killing.100% means all animals all is killed; 0% then means no animal is killed.
In this test, the compound that for example prepares example I b-13 demonstrated 100% killing rate after 2 days under 0.1% activity compound concentration of demonstration.
Table F
To the deleterious insect mythimna separata test of plant
Figure A9419460600971
Embodiment G
Fly is tested tested animal: the house fly, WHO (N) plants solvent: 35 weight part glycol monomethyl methyl ethers
35 weight part nonyl phenol polyglycol ethers
For the preparation appropriate formulation, three weight part active compounds are mixed with seven parts of above-mentioned solvent/emulsifier mixtures, and the missible oil that forms is diluted with water to desirable in all cases concentration.
The above-mentioned preparation of 2ml active compound is drawn to is arranged in the accompanying on the round filter paper (φ 9.5cm) in Ti Shi (Petri) culture dish of suitable size.After the filter paper drying, supply the examination animal to draw with 25 and receive in the Petri culture dish, then culture dish is covered.
After 6 hours, measure the activity of active agent preparations.Activity is represented with %.100% means all flies all is killed; 0% no fly of expression is killed.
In this test, the compound that for example prepares example I b-4, Ib-5, Ib-6 and Ib-12 demonstrates 100% killing rate under the 1000ppm activity compound concentration of demonstration.
Table G
The fly test
Embodiment H
The blattaria test: Groton bug, periplaneta america is for trying animal: solvent: 35 weight part glycol monomethyl methyl ethers
35 weight part nonyl phenol polyglycol ethers
For the preparation appropriate formulation, three weight part active compounds are mixed with seven parts of above-mentioned solvent/emulsifier mixtures, and formed missible oil is diluted with water to desirable in each case concentration.
The above-mentioned preparation of 2ml active compound is drawn on the round filter paper in the Petri culture dish that is arranged in suitable size on (φ 9.5cm).After the filter paper drying, 5 Groton bugs or periplaneta america are gone in the Petri culture dish, hide then and go up culture dish.
After 3 days, measure the activity of active agent preparations.Activity is represented with %.100% is meant that all blattarias all are killed; 0% represents that then no blattaria is killed.
In this test, the compound that for example prepares example I b-4, Ib-6 and Ib-12 demonstrates 100% killing rate under the 1000ppm activity compound concentration of demonstration.
Table H
The blattaria test
Figure A9419460601011

Claims (20)

1. aryl-trifluoromethyl imidazoles of replacing of formula (I) N-:
Figure A9419460600021
Wherein Ar represents the aryl that replaces arbitrarily, and W represents haloalkyl, one of the aryl of any replacement of R representative or following radicals :-OR 1,-SR 1Or-N (R 2COR 3And Y represents halogen, trifluoromethyl, nitro ,-S (O) nR 6Or the aryl that replaces arbitrarily,
In addition, when Y is positioned on the C-2 position of imidazole ring, also represent CN or-CONR 4R 5, R wherein 1The following radicals of representing hydrogen or representative to replace arbitrarily: alkyl, cycloalkyl, alkenyl, alkynyl, aryl or aralkyl, R 2The aryl of representing hydrogen, alkyl, haloalkyl, cycloalkyl or replacing arbitrarily, R 3Representative (X) mR 7, X represent O, S or-NR 8, m represents 0 or 1, R 4, R 5And R 8Represent hydrogen independently of one another, alkyl or the aryl that replaces arbitrarily, R 6Represent alkyl, haloalkyl or the aryl and the R that replace arbitrarily 7Represent alkyl, haloalkyl or the aryl that replaces arbitrarily in all cases, aralkyl or heteroaryl and n represent 0,1 or 2.
2. the described formula of claim 1 (I) compound, described compound is for having structure (Ia), (Ib) or compound (Ic):
Figure A9419460600031
Wherein Ar, W, P and Y have meaning described in the claim 1.
3. the described formula of claim 1 (I) compound, wherein: Ar represents C 6-C 10Aryl, this group is selected from halogen, nitro, cyano group, C 1-C 12Alkyl, C 1-C 12Alkylthio, C 1-C 12Alkoxyl group, any divalence two oxyalkylenes that replace ,-OCF 2Z ,-S (O) 1CF 2Z and-CFR 9R 10Arbitrarily single replace or polysubstituted of identical or different substituting group.W represents C 1-C 6Haloalkyl.R represents phenyl, and this group is by halogen, cyano group, nitro, C 1-C 6Alkyl, C 1-C 6Haloalkyl or C 1-C 6Alkoxyl group is single arbitrarily to be replaced to three replacements, perhaps is group-OR 1,-SR 1With-N (R 2) COR 3One of.Y represent halogen, trifluoromethyl, nitro ,-S (O) nR 6, or C 6-C 10Aryl, this group is selected from halogen, cyano group, nitro, any divalence two oxyalkylenes that replace ,-OCF 2Z ,-S (O) nCFR 9R 10With-CFR 9R 10Identical or different substituting group arbitrarily single replacement to three replace, in addition, when Y is positioned on the C-2 position of imidazole ring, also represent CN or-CONR 4R 5R 1Represent hydrogen, C 1-C 6Alkyl, C 1-C 4-alkoxy-C 1-C 6-alkyl, C 1-C 6-haloalkyl, C 3-C 6Cycloalkyl, C 2-C 6Alkenyl, C 2-C 6Halogenated alkenyl, C 2-C 6Alkynyl, C 2-C 6The halo alkynyl, or be phenyl or benzyl, described phenyl or benzyl are selected from halogen, C separately 1-C 6Alkyl and C 1-C 6The identical or different substituting group of alkoxyl group is single arbitrarily to be replaced to three replacements.R 2Represent hydrogen, C 1-C 6Alkyl, C 1-C 6Haloalkyl, C 3-C 6Cycloalkyl, or be phenyl, this phenyl is by halogen, C 1-C 6Alkyl or C 1-C 6Alkoxyl group is single arbitrarily to be replaced to three replacements.R 3Representative (X) mR 7X represents O.M represents 0 or 1.R 4And R 5Represent hydrogen, C independently of one another 1-C 6Alkyl, or be phenyl, it is selected from
Halogen and C 1-C 6The identical or different substituting group of alkyl is single arbitrarily to be replaced to three replacements
Phenyl.R 6Represent C 1-C 6Alkyl, C 1-C 6Haloalkyl, or be phenyl, this benzene
Base can be selected from halogen, C 1-C 6Alkyl and C 1-C 6Alkoxyl group identical or
The different substituents list replaces to three replacements.R 7Represent C 1-C 6Alkyl, C 1-C 6Haloalkyl, or be phenyl or benzyl,
Described phenyl or benzyl separately can be by halogens, C 1-C 6Alkyl, C 1-C 6Alkane
Oxygen base, trifluoromethyl, cyano group or nitro are single arbitrarily to be replaced to three replacements, or the expression pyridine
Base or picolyl, they are selected from halogen, C separately 1-C 6Alkyl and C 1-C 6
The identical or different substituting group of alkoxyl group is single arbitrarily to be replaced to three replacements.R 9And R 10The hydrogen or halogen of representing independently of one another.Z represents hydrogen, halogen or C 1-C 6Haloalkyl.L represents 0,1 or 2.N represents 0,1 or 2.
4. the described formula of claim 1 (I) compound, wherein Ar represents phenyl, this phenyl is selected from single arbitrarily the replacement to three replacements of identical or different substituting group of divalence two oxyalkylenes with 1 to 4 carbon atom that halogen, nitro, cyano group and halogen replace arbitrarily, or at most by-OCF 2Z ,-S (O) 1CF 2Z or-CFR 9R 10Two replace.W represents C 1-C 4Alkyl, this group can be replaced by fluorine or chlorine.R represents group-OR 1, SR 1,-N (R 2) COR 7Or-N (R 2) CO 2R 7One of.Y represent halogen, trifluoromethyl, nitro ,-S (O) nR 6, or be phenyl, this phenyl be selected from halogen, cyano group, nitro ,-OCF 2Z ,-S (O) nCFR 9R 10With-CFR 9R 10Identical or different substituting group arbitrarily single replacement to three replace, in addition, when Y is positioned on the 2-position of imidazole ring, also represent CN or-CONR 4R 5R 1Represent hydrogen, or representative is by 1 to 3 fluorine and/or chlorine atom or the C that replaced arbitrarily by methoxy or ethoxy 1-C 4-alkyl, or be C 3-C 6Cycloalkyl, C 2-C 4Alkenyl, C 2-C 4Alkynyl, C 2-C 4Halogenated alkenyl, C 2-C 4The halo alkynyl, or be phenyl, described phenyl is selected from F, Cl, Br, C 1-C 4Alkyl and C 1-C 4The identical or different substituting group of alkoxyl group is single arbitrarily to be replaced to three replacements.R 2Represent hydrogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 3-C 6Cycloalkyl, or be phenyl, this phenyl can be selected from fluorine, chlorine, bromine, C 1-C 4Alkyl and C 1-C 4The identical or different substituting group of alkoxyl group is single arbitrarily to be replaced to three replacements.R 4And R 5Hydrogen, the C of representing independently of one another 1-C 4Alkyl, or be phenyl, this phenyl is selected from fluorine, chlorine, bromine and C 1-C 4The identical or different substituting group of-alkyl is single arbitrarily to be replaced to three replacements.R 6Represent methylidene, the identical or different substituting group list that it can be selected from fluorine, chlorine and/or bromine replaces to three replacements.-N (R 2) CO 2R 7In R 7Represent C 1-C 4Alkyl.-N (R 2) COR 7In R 7Represent halogen to replace C arbitrarily 1-C 4Alkyl,
Or be phenyl or pyridyl, described phenyl or pyridyl be selected from separately fluorine, chlorine, bromine,
C 1-C 4Alkyl and C 1-C 4The identical or different substituting group of alkoxyl group is single arbitrarily
Replacement to three replaces.R 9And R 10Hydrogen, fluorine, the chlorine or bromine represented independently of one another.Z represents hydrogen, fluorine, chlorine or C 1-C 4Alkyl, described alkyl is by fluorine and/or chlorine list replacement or polysubstituted.L represents 0 or 1.N represents 0,1 or 2.
5. the described formula of claim 1 (I) compound, wherein Ar represents phenyl, described phenyl be selected from fluorine, chlorine, bromine, nitro, cyano group and
Have 1 or 2 carbon atom and by 1 to 4 fluorine and/or chlorine atom replace arbitrarily two
The identical or different substituting group of valency two oxyalkylenes is single arbitrarily to be replaced to three replacements, or at most
Quilt-OCF 2Z ,-S (O) 1CF 2Z or-CFR 9R 10Two replace, and W represents CF 3Or C 2F 5, R represents Shi-OR 1,-SR 1,-N (R 2) CO 2R 7Or-NHCOR 7Group.Y represents chlorine, bromine, trifluoromethyl, nitro or phenyl, and this phenyl is selected from
Fluorine, chlorine, bromine, cyano group, nitro ,-OCF 2Z ,-S (O) nCF 9R 10With
-CFR 9R 10Any Dan Zhisan of identical or different substituting group replace R 1Represent methylidene, ethyl, just-or sec.-propyl or just-, secondary-, exclusive OR
Tert-butyl, they are separately by one to three fluorine and/or chlorine atom or any by methoxyl group
Replace, or be cyclopropyl, cyclopentyl, 2-propenyl, crotyl, 4-chlorine
-crotyl, 2-propynyl or 4-chloro-crotyl, or be can quilt
The optional phenyl that replaces of fluorine, chlorine, bromine, methoxyl group or methyl, R 2Represent hydrogen, or be methyl, ethyl, just-or different-propyl group or just-, secondary-, different-
Or tert-butyl, they are replaced arbitrarily by one to three fluorine and/or chlorine atom separately, or
Be cyclopropyl or cyclopentyl, or be phenyl that this phenyl is selected from fluorine, chlorine, bromine, methyl
Any Dan Zhisan replaces with the identical or different substituting group of methoxyl group ,-N (R 2) CO 2R 7In R 7Represent methylidene, ethyl, just-or different-propyl group or
Just-, secondary-, exclusive OR tert-butyl ,-NHCOR 7In R 7Represent methylidene, ethyl, just-or different-propyl group or just-, secondary-, the exclusive OR tert-butyl, they can be replaced arbitrarily by 1 to 3 fluorine and/or chlorine atom separately, or be phenyl, that this phenyl can be selected from the identical or different substituting group of fluorine, chlorine, bromine, methyl and methoxyl group is arbitrarily single-to three-replace R 9And R 10Represent hydrogen, fluorine or chlorine, Z to represent fluorine, fluorine, chlorine, difluoromethyl, trifluoromethyl, fluorine chloro methyl or formula-CHFCF independently of one another 3Base, l represents 0, and n represents 0 or 1.
6. the preparation method of the described formula of claim 1 (I) N-substituted aryl trifluoromethyl imidazoles, this method comprises formula (II) imidazoles
Figure A9419460600081
Wherein, Ar, the definition of W and Y is the same, with the reaction of formula (III) compound,
V-CH 2-R (III) wherein the same and V of the definition of R represents the negatively charged ion leavings group, if suitable, if the above-mentioned acid acceptor that is reflected at would exist down and is suitably in thinner and carries out under existing.
7. the 2-aryl-4 of formula (IIa-a), 5-two (trifluoromethyl) imidazoles:
Figure A9419460600091
Wherein the definition of Ar and W is described with claim 1.
8. the preparation method of the described formula of claim 7 (IIa-a) glyoxaline compound, this method comprises formula (IV) benzamidine
Figure A9419460600092
Wherein the definition of Ar is described with claim 1, with the reaction of formula V compound,
Figure A9419460600093
Wherein the definition of W is same as above, if suitable, the above-mentioned thinner that is reflected at exists down and carries out: and if in the presence of alkali and suitable formula (VIa) that cyclisation generated in the presence of thinner or (VIb) compound:
Figure A9419460600101
Wherein the definition of Ar and W is the same.
9. formula (IIb-a) imidazoles
Figure A9419460600102
Ar wherein 1Represent substituted aryl, described in the definition of Ar in the suitable substituents see claim 3, Y 1Represent halogen, nitro or group-S (O) nR 6, wherein, R 6The same with the definition of n, and the definition of W is described with claim 1.
10. the preparation method of the described formula of claim 9 (IIb-a) imidazoles, this method comprises makes formula (VII) compound carry out following reaction:
Figure A9419460600111
Ar wherein 1And the definition of W is described with claim 9,
(a) with the nitrating agent reaction, if suitably in the presence of thinner, carry out, or
(b) with the reaction of formula (XIII) sulfenyl chlorine,
R 6SCI (XIII) is R wherein 6Definition the same, if the suitably above-mentioned thinner that is reflected at exists down and carries out, and if suitable, with formula (IIb-b) compound that rear oxidation generated:
Figure A9419460600112
R wherein 6, the definition of W and n is the same, or
(c) they and halogenating agent are reacted, if suitably in the presence of thinner, carry out.
11. formula (IIc-a) imidazoles
Figure A9419460600121
Wherein the definition see claim 1 of Ar and W is described, and Y 3Represent halogen, cyano group or group-CONR 4R 5, R wherein 4And R 5Definition see claim 1 described.
12. the preparation method of the described formula of claim 11 (IIc-a) imidazoles, this method comprise that the first step makes formula (VIII) imidazoles Wherein the definition of Ar and W is described with claim 1, with halogenating agent reaction, if suitably, formula (IIc-b) imidazoles and CuCN and the KCN mixture that is generated was carried out for second step react: Wherein the same and Hal of the definition of Ar and W represents halogen,
Perhaps make formula (VIII) compound
Figure A9419460600131
Wherein the definition of Ar and W is the same, at first with the reaction of formula (XVIII) compound,
Pg-Hal (XVIII) wherein Pg represents that protecting group and Hal represent chlorine or bromine, if suitably, if above-mentioned thinner such as the acetonitrile of being reflected at exists down and suitably carries out in the presence of alkali,
With formula (XIV) compound that is generated Ar wherein, the definition of W and Pg is the same, and the metallizing thing reacts in the presence of thinner, then with N, N-two substituted formyl sulfonamide derivativess, if suitably reaction in the presence of thinner, subsequently with formula (XV) compound and the azanol reaction that are generated: Ar wherein, the definition of W and Pg is the same, if if the suitably above-mentioned thinner that is reflected at exists down and suitably carries out in the presence of alkali,
Formula (XVI) oxime that is generated is handled with dewatering agent:
Figure A9419460600142
Ar wherein, the definition of W and Pg is the same,
Last formula (XVII) compound that heating is generated in the presence of acid: Ar wherein, the definition of W and Pg is the same,
Formula (IIc-c) imidazoles that in the presence of acid, is generated above the hydrolysis:
Figure A9419460600151
Wherein the definition of Ar and W is the same,
Transform formula (IIc-d) compound that is generated and become corresponding acyl chlorides:
Figure A9419460600152
Wherein the definition of Ar and W is the same, and these acyl chlorides and following formula (IX) amine are reacted:
HNR 4R 6(IX) R wherein 4And R 5Definition the same, if if suitable reactions be in the presence of thinner and be suitably in the presence of the acid acceptor and carry out.
13. formula (IIc-e) imidazoles
Figure A9419460600153
Ar wherein 1And the definition of W is described with claim 9.
14. comprising, the preparation method of the described formula of claim 13 (IIc-e) imidazoles, this method make formula (X) compound Ar wherein 1And the definition of W is the same, with formula (XI) the trifluoro acetaldehyde ethanol that contracts
Figure A9419460600162
If in the presence of amine acetate and be suitably in the presence of the thinner and react.
15. formula (IIc-f) imidazoles Ar wherein 1And the same and Ar of definition of W 2The aryl that representative replaces arbitrarily, described in the definition of Ar in the suitable substituting group see claim 3.
16. comprising, the preparation method of the described formula of claim 15 (IIc-f) imidazoles, this method make formula (X) compound Ar wherein 1And the definition of W is the same, with formula (XII) aldehyde
Ar 2-CHO (XII) is Ar wherein 2Definition the same, if in the presence of ammonium acetate and be suitably in the presence of the thinner reaction.
17. an agricultural chemicals, described agricultural chemicals comprise aryl-trifluoromethyl imidazoles that the described formula of at least a claim 1 to 5 (I) N-replaces.
18. aryl-trifluoromethyl imidazoles that the described formula of claim 1 to 5 (I) N-replaces is used to kill animal pest.
19. kill the method for animal pest, this method comprises that aryl-trifluoromethyl imidazoles that the described formula of claim 1 to 5 (I) N-is replaced acts on animal pest and/or their environment.
20. prepare the method for agricultural chemicals, this method comprises that aryl-trifluoromethyl imidazoles that the described formula of claim 1 to 5 (I) N-is replaced mixes with extender and/or tensio-active agent.
CN94194606A 1993-12-21 1994-12-08 N-substituted aryl trifluoromethyl imidazoles Pending CN1138326A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4343613A DE4343613A1 (en) 1993-12-21 1993-12-21 N-substituted aryl trifluoromethylimidazoles
DEP4343613.7 1993-12-21

Publications (1)

Publication Number Publication Date
CN1138326A true CN1138326A (en) 1996-12-18

Family

ID=6505620

Family Applications (1)

Application Number Title Priority Date Filing Date
CN94194606A Pending CN1138326A (en) 1993-12-21 1994-12-08 N-substituted aryl trifluoromethyl imidazoles

Country Status (6)

Country Link
EP (1) EP0736013A1 (en)
JP (1) JPH09506876A (en)
CN (1) CN1138326A (en)
AU (1) AU1242795A (en)
DE (1) DE4343613A1 (en)
WO (1) WO1995017390A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102408376A (en) * 2011-10-21 2012-04-11 浙江工业大学 Synthesis method of tetra-substituted iminazole
CN106164065A (en) * 2014-03-28 2016-11-23 先正达参股股份有限公司 Have sulfur-bearing substituent group kills harmful organism active heterocycles derivant
CN107162982A (en) * 2017-06-19 2017-09-15 广东药科大学 Imidazole compounds with anticancer activity and derivatives thereof

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19613172A1 (en) * 1996-04-02 1997-10-09 Bayer Ag Use of substituted aryl-imidazoles
DE19623207A1 (en) * 1996-06-11 1997-12-18 Bayer Ag Imidazole derivatives
FR2753377B1 (en) * 1996-09-19 1999-09-24 Rhone Merieux NOVEL PARASITICIDE ASSOCIATION BASED ON 1-N-PHENYLPYRAZOLES AND ENDECTOCIDAL MACROCYCLIC LACTONES
EP3766871A1 (en) * 2014-08-13 2021-01-20 Nippon Soda Co., Ltd. Diarylimidazole compound and pest control agent
WO2018052119A1 (en) 2016-09-16 2018-03-22 住友化学株式会社 Heterocyclic compound, and harmful-arthropod-controlling agent containing same

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54148788A (en) * 1978-05-15 1979-11-21 Takeda Chem Ind Ltd 1,2-disubstituted-4-halogenoimidazole-5-acetic acid derivative and its preparation
GB2144408A (en) * 1983-08-04 1985-03-06 Tanabe Seiyaku Co Imidazole derivatives
IL85556A (en) * 1987-03-05 1994-06-24 May & Baker Ltd Pesticidal method using 2-phenylimidazole derivatives, some such novel compounds and process for their preparation
IL86134A (en) * 1987-05-02 1993-06-10 Basf Ag N-substituted azoles, their manufacture and their use as pesticides and compositions containing them
US5013847A (en) * 1988-07-29 1991-05-07 Basf Aktiengesellschaft Phenoxyalkyl-substituted heteroaromatics and a method for controlling pests
ES2131104T3 (en) * 1992-01-29 1999-07-16 Du Pont SUBSTITUTED PHENYLHETEROCIDIC HERBICIDES COMPOUNDS.

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102408376A (en) * 2011-10-21 2012-04-11 浙江工业大学 Synthesis method of tetra-substituted iminazole
CN102408376B (en) * 2011-10-21 2014-01-29 浙江工业大学 Synthesis method of tetra-substituted iminazole
CN106164065A (en) * 2014-03-28 2016-11-23 先正达参股股份有限公司 Have sulfur-bearing substituent group kills harmful organism active heterocycles derivant
CN106164065B (en) * 2014-03-28 2019-05-10 先正达参股股份有限公司 Harmful organism active heterocycles derivative is killed with sulfur-bearing substituent group
CN107162982A (en) * 2017-06-19 2017-09-15 广东药科大学 Imidazole compounds with anticancer activity and derivatives thereof
CN107162982B (en) * 2017-06-19 2020-02-11 广东药科大学 Imidazole compounds with anticancer activity and derivatives thereof

Also Published As

Publication number Publication date
DE4343613A1 (en) 1995-06-22
JPH09506876A (en) 1997-07-08
AU1242795A (en) 1995-07-10
EP0736013A1 (en) 1996-10-09
WO1995017390A1 (en) 1995-06-29

Similar Documents

Publication Publication Date Title
CN1216030C (en) O-acyl-alpha-hydroxycarboxylic ester compound and its preparation method
CN1039079C (en) Pesticidal 1-arylpyrroles
CN1075060C (en) Alkoxy-alkyl-substd. 1-H-3-aryl-pyrrolidine-2,4-diones used as herbicides and pesticides
CN1167683C (en) Arylpyrozole insecticides
CN1128802C (en) Phenyl-substituted cyclic ketoenol
CN1115344C (en) Novel substituted phenyl keto enols
CN1069900C (en) Pesticide
CN1926129A (en) Novel insecticides
CN1129444A (en) Substituted aryl-keto-enolic heterocycles
CN1140449A (en) N-pyrazolyl anilines and N-pyrazolyl aminopyridines as pesticides
CN1533389A (en) Azole derivatives useful as insecticide
CN1121399C (en) Isothiazolcarboxylic acid derivatives
CN1780825A (en) Insecticidal (dihalopropenyl) phenylalkyl substituted dihydrobenzofuran and dihydrobenzopyran derivatives
CN1487920A (en) Deltal-pyrrolines used as pesticides
CN1112849C (en) Use of 1,2,3-thiadiazole carboxylic acid (thio) esters for the control of pests and novel 1,2,3-thiadiazole carboxylic acid (thio) esters
CN1384832A (en) Pesticidal aminoheterocyclamide compounds
CN1384826A (en) Pesticidal N-heteroaryl alpha-alkoximino-carboxamides
CN1138860A (en) 1,2,3,4-tetrahydro-5-nitro-pyrimidines substituees
CN1503805A (en) Salts of avermectins substituted in the 4&#39;&#39;-position and having pesticidal properties
CN1138326A (en) N-substituted aryl trifluoromethyl imidazoles
CN1171880C (en) Pesticidal triazine derivatives
CN1219759C (en) Intermediate for preparing substitated biphenyl oxazoline compounds
CN1113238A (en) Substituted pyrazoline derivatives
ES2229266T3 (en) PROCEDURE FOR OBTAINING 5,6-DIHYDRO-1,3-OXAZINES.
CN1131417A (en) Substituted 4-carbamoyl pyrrolin-2-one and dihydrofuran-2-one derivatives and their use as pesticides

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C01 Deemed withdrawal of patent application (patent law 1993)
WD01 Invention patent application deemed withdrawn after publication